CN109476561A

CN109476561A - Capsule comprising being used as the benzyl propargyl ether of nitrification inhibitor

Info

Publication number: CN109476561A
Application number: CN201780043911.4A
Authority: CN
Inventors: K-H·施奈德; B·纳韦; R·H·斯塔夫; A·维瑟迈尔
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2016-05-18
Filing date: 2017-05-15
Publication date: 2019-03-15
Also published as: BR112018073298A2; EP3458433A1; AU2017267129A1; ZA201808345B; CA3024100A1; AR108517A1; JP2019520293A; WO2017198588A1; US20190276376A1; RU2018143590A; CL2018003267A1; MX2018014176A

Abstract

Capsule comprising being used as the benzyl propargyl ether of nitrification inhibitor.The present invention relates to the capsules comprising (1) core (a) and shell (b) or (2) matrix (c), wherein, in the case where option (1), core (a) includes the benzyl propargyl ether compound of Formulas I and shell (b) includes shell material；And in the case where option (2), matrix (c) includes the benzyl propargyl ether compound and host material of Formulas I.

Description

Capsule comprising being used as the benzyl propargyl ether of nitrification inhibitor

The present invention relates to the capsules comprising (1) core (a) and shell (b) or (2) matrix (c), wherein option (1) the case where Under, core (a) includes the benzyl propargyl ether compound of Formulas I and shell (b) includes shell material；And in the case where option (2), matrix (c) comprising the benzyl propargyl ether compound and host material of Formulas I.The invention further relates to the capsules comprising capsule of the present invention Suspension, the mixture comprising fertilizer and capsule of the present invention or capsule suspension liquid.In addition, the present invention relates to purposes and method, packet Include application capsule, capsule suspension liquid and mixture of the present invention.

Nitrogen is the indispensable element of plant growth and breeding.About 25% plant can utilize nitrogen (ammonium and nitrate) source in soil From the decomposable process (mineralising) of organonitrogen compound such as humus, plant and animal residue and organic fertilizer.About 5% is derivative In rainfall.However, largest portion (70%) supplies plant by inorganic nitrogeneous fertilizer in global basis.Leading nitrogenous fertilizer to be used includes Nearly 90% is in NH in the nitrogenous fertilizer of ammonium compounds or derivatives thereof, the i.e. whole world supply₄ ⁺Form (Subbarao etc., 2012, Advances in Agronomy, 114,249-302).This is particularly due to NH₄ ⁺Assimilation is than other nitrogen sources such as NO₃ ^-Assimilation exist The fact that more effective on energy.

Further, since for cation, NH₄ ⁺It is protected by the functional group electrostatic of electronegative surface of clay and soil organic matter It holds.The combination is by force to being enough to limit by leaching into the NH in underground water₄ ⁺Loss.On the contrary, electronegative NO₃ ^-It will not be with soil In conjunction with and be easy to sweeten off from the root zone of plant.In addition, nitrate anion may lose because of denitrification, and denitrification is by nitric acid Root and nitrite anions (NO₂ ^-) microorganism conversion at gaseous form nitrogen such as nitrous oxide (N₂) and dinitrogen (N O₂)。

However, ammonium (NH₄ ⁺) compound converts in relative short time during being known as nitrification by edaphon For nitrate anion (NO₃ ^-).Nitrification is mainly by two class chemolithotrophic bacterias-Nitromonas (Ni-trosomonas) and nitre Change Bacillus (Nitrobacter) ammonia oxidizing bacteria (AOB), they for soil bacteria population generally existing component-into Row.The basic enzyme for being responsible for nitrification is ammona monooxygenase (AMO), also found in ammoxidation archaeal (Subbarao etc., 2012, Advances in Agronomy, 114,249-302).

The nitration method typically results in nitrogen leakage and environmental pollution.Due to various losses, the nitrogenous fertilizer of application about 50% exists Loss is (see Nelson and Huber in that year after fertilizer addition；Maize production nitrification inhibitor (2001), National Corn Handbook, Iowa State University).

It as countermeasure, proposes using nitrification inhibitor, is used together with fertilizer.Suitable nitrification Inhibitor includes biological nitration inhibitor (BNI), as linoleic acid, alpha-linolenic acid, p-Coumaric Acid methyl esters, Ferulic acid methylester, MHPP, Karanjin, brachialacton or 1,4-benzoquinone sorgoleone (Subbarao etc., 2012, Advances in Agronomy, 114,249-302).Other suitable nitrification inhibitors are synthesis chemical inhibitor, such as N-Serve (Nitrapyrin), dicyandiamide (DCD), 3,4- dimethyl pyrazole phosphate (DMPP), 4- amino -1,2,4- triazole hydrochloride (ATC), the chloro- 6- methylpyrimidine (AM) of 1- amide groups -2- thiocarbamide (ASU), 2- amino -4-, trichloromethyl -1 5- ethyoxyl -3-, 2,4- thiadiazoles (tetrazolium) or 2- sulphathiazole (ST) (Slangen and Kerkhoff, 1984, Fertilizer research, 5 (1), 1-76).

In addition, pyrazolyl nitrification inhibitor for example has been described and US 3,635,690, WO 2011/009572, WO In 2011/015305, DE 10 2,011 120 098 and DE, 10 2,013 022 031 B3.

However, many in these inhibitor only works to non-optimal.It is estimated in next 20-30 world population To significantly it increase, it is therefore desirable to the food production of sufficient amount and enough quality.In order to realize this, the use to the year two thousand fifty nitrogenous fertilizer will It is double.Due to environment reason, this is not possible because the eutrophication of nitrate concentration, surface water in drinking water and Gas, which is discharged into air, has had reached critical level in many places, so as to cause water pollution and air pollution.However, if Using nitrification inhibitor, then effect of fertilizer significantly improves and less fertilizer therefore can be used.Therefore, novel nitre is clearly required Change inhibitor and the method using them.

Since certain nitrification inhibitors have also the drawback that, such as since they can cause environmental problem, largely ground Study carefully to find to show other active compounds categories as nitrification inhibitor.

In this regard, had been found that acetylene is effective nitrification inhibitor before more than 30 years.However, because acetylene is gas, It never obtains any practical value as nitrification inhibitor.G.W.McCarty etc. is described through acetylene compound such as benzene Ethyl-acetylene inhibits to nitrify (Soil Sci.Soc.Am.J., volume 50,1986, the 1198-1201 pages) in the soil.Phenylacetylene Nitrification inhibitor is also been described as in 4,552,581 A of US.However, phenylacetylene is unsatisfactory for the present invention for example with regard to low application High activity demand under rate.

Since phenylacetylene, it has been found that benzyl propargyl ether is suitable as nitrification inhibitor, and shows to be higher than phenyl The activity of acetylene.

However, benzyl propargyl ether has high-vapor-pressure, it may be, for example, 0.2-2Pa at 2 DEG C.The height of benzyl propargyl ether Vapour pressure causes difficulty in terms of the suitable formulations that conveying can provide long-term nitrification inhibitory activity in the soil.

Therefore, the purpose of the present invention is to provide be suitable as nitrification inhibitor and overcome the volatilization of active constituent in the environment Property loss benzyl propargyl ether preparaton.It is a further object of the present invention to provide include active constituent (i.e. formula (I) chemical combination Object) capsule, cause when being applied to soil enhancing nitrification inhibitory activity.It is yet another object of the invention to provide have length The capsule formulation comprising formula (I) compound of phase nitrification inhibitory activity.

The present invention solves the needs and is related to capsule, it includes:

(1) core (a) and shell (b), center (a) are encapsulated by shell (b)；Or

(2) matrix (c)；

Wherein, if capsule includes core (a) and shell (b) according to option (1), core (a) includes compound of formula I or it is three-dimensional Isomers, salt, tautomer or N- oxide:

Wherein

R¹And R²It is independently selected from H, C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkynyl, C₁-C₆Halogenated alkyl, C₁-C₄ Alkoxy -C₁-C₄Alkyl, C₁-C₆Alkoxy, C₂-C₆Alkenyloxy, C₂-C₆Alkynyloxy group, wherein carbon atom in each case may be used With unsubstituted or 1,2 or 3 identical or different substituent R can be had^e；

C₃-C₈Naphthenic base, C₃-C₈Cycloalkenyl, heterocycle, aryl, heteroaryl, C₃-C₈Naphthenic base-C₁-C₆Alkyl, C₃-C₈Ring Alkenyl-C₁-C₆Alkyl, heterocycle-C₁-C₆Alkyl, aryl-C₁-C₆Alkyl and heteroaryl-C₁-C₆Alkyl, phenoxy group and benzyloxy, Wherein cyclic moieties in each case can be unsubstituted or can be identical or different with 1,2,3,4 or 5 Substituent R^a；

A is phenyl, wherein the benzyl ring can it is unsubstituted or can with 1,2,3,4 or 5 it is identical or different Substituent R^A；

Wherein

R^ASelected from CN, halogen, NO₂、OR^b、NR^cR^d、C(Y)R^b、C(Y)OR^b、C(Y)NR^cR^d、S(Y)_mR^b、S(Y)_mOR^b,

C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkynyl, C₁-C₆Halogenated alkyl, C₁-C₆Alkoxy, C₁-C₆Alkylthio group, Middle carbon atom in each case can be unsubstituted or can have 1,2 or 3 identical or different substituent R^e；

C₃-C₈Naphthenic base, C₃-C₈Cycloalkenyl, heterocycle, aryl, heteroaryl, C₃-C₈Naphthenic base-C₁-C₆Alkyl, C₃-C₈Ring Alkenyl-C₁-C₆Alkyl, heterocycle-C₁-C₆Alkyl, aryl-C₁-C₆Alkyl and heteroaryl-C₁-C₆Alkyl, phenoxy group and benzyloxy, Wherein cyclic moieties can be unsubstituted or can have 1,2,3,4 or 5 identical or different substituent R^a；

And wherein

R^aSelected from CN, halogen, NO₂、C₁-C₄Alkyl, C₁-C₄Halogenated alkyl and C₁-C₄Alkoxy；

Or two substituent Rs on adjacent carbon atom^aIt can be for selected from CH₂CH₂CH₂CH₂、OCH₂CH₂CH₂、 CH₂OCH₂CH₂、OCH₂CH₂O、OCH₂OCH₂、CH₂CH₂CH₂、CH₂CH₂O、CH₂OCH₂、O(CH₂)O、SCH₂CH₂CH₂、 CH₂SCH₂CH₂、SCH₂CH₂S、SCH₂SCH₂、CH₂CH₂S、CH₂SCH₂、S(CH₂) S bridge and with the two R^aThe carbon being bonded Atom is formed together 5 Yuans or 6 Yuans saturated carbon rings or heterocycle；

R^bSelected from H, C₁-C₆Alkyl, C₂-C₄Alkenyl, C₂-C₄Alkynyl, C₁-C₄Halogenated alkyl, phenyl and benzyl；

R^cAnd R^dIt is independently selected from H, C₁-C₄Alkyl and C₁-C₄Halogenated alkyl；Or

R^cAnd R^dThe N atom being bonded with them is formed together 5 or 6 Yuans saturations or unsaturated heterocycle, the heterocycle and can have Another hetero atom selected from O, S and N as ring members atom and wherein the heterocycle can it is unsubstituted or can with 1,2, 3,4 or 5 substituent groups for being independently selected from halogen；

R^eSelected from CN, halogen, C₁-C₄Alkyl, C₁-C₄Halogenated alkyl, C₁-C₄Alkoxy and C₁-C₄Halogenated alkoxy；

Y is O or S；And

M is 0,1 or 2；

And

Shell (b) includes shell material, is selected from:

(b1) polyaddition products of isocyanates；

(b2) poly- (methyl) acrylate；With

(b3) aminoplast；

And wherein, if capsule includes matrix (c) according to option (2), matrix (c) includes compound of formula I or it is vertical Body isomers, salt, tautomer or N- oxide:

Wherein

C₃-C₈Naphthenic base, C₃-C₈Cycloalkenyl, heterocycle, aryl, heteroaryl, C₃-C₈Naphthenic base-C₁-C₆Alkyl, C₃-C₈Ring Alkenyl-C₁-C₆Alkyl, heterocycle-C₁-C₆Alkyl, aryl-C₁-C₆Alkyl and heteroaryl-C₁-C₆Alkyl, phenoxy group and benzyloxy, Wherein cyclic moieties can be unsubstituted or can have 1,2,3,4 or 5 identical or different substituent R^a；And Wherein

Y is O or S；And

M is 0,1 or 2；

And host material, it is selected from:

(c1) poly- (methyl) acrylate；With

(c2) calcium alginate.

Surprisingly, it was found that if the above-mentioned capsule comprising active constituent (i.e. formula (I) compound) is applied to soil, It improves nitrification with can dramatically inhibit, compared to application non-encapsulated active constituent.

Particularly, if applying capsule according to the present invention, the long period of activity that may refrain from for nitrification can be improved.

Obviously, the controlled release of active constituent can also be provided in certain embodiments of the present invention.

Capsule can be applied to the root zone of plant, soil, soil substitute and/or wherein plant growth or be intended to grow Place；Or it is applied to fertilizer, the composition comprising fertilizer or the particle comprising fertilizer.

Capsule provides preferably in the form of capsule suspension liquid.

Therefore, the invention further relates to a kind of capsule suspension liquid, it includes:

It include the suspended phase of capsule of the present invention, wherein capsule has 300 μm or smaller mass median particle size；With

Water phase；

Wherein the ratio between suspended phase and water phase are preferably 1:0.5-1:20.

Capsule suspension liquid can be applied to the root zone of plant, soil, soil substitute and/or wherein plant growth or be intended to raw Long place；Or it is applied to fertilizer, the composition comprising fertilizer or the particle comprising fertilizer.

The invention further relates to a kind of mixture, it includes:

(i) inorganic support particles, organic carrier particle, fertilizer, the composition comprising fertilizer or the particle comprising fertilizer；With

(ii) capsule according to the present invention or capsule suspension liquid according to the present invention.

In addition, the present invention relates to capsules according to the present invention, capsule suspension liquid according to the present invention or according to the present invention Purposes of the mixture in agriculture chemistry application, wherein the purposes preferably includes to apply capsule or capsule suspension liquid or mixture For the root zone of plant, soil, soil substitute and/or wherein plant growth or be intended to grow place.Purposes is preferred for Reduce nitrification.

Therefore, the invention further relates to a kind of methods for reducing nitrification, including capsule or capsule suspension liquid or mixture are applied For the root zone of plant, soil, soil substitute and/or wherein plant growth or be intended to grow place.

Hereafter by capsule of the present invention, capsule suspension liquid and mixture and including its application purposes and method make into one Step detailed description.

Before detailed description of the present invention exemplary implementation scheme, provide for understanding the important definition of the present invention.

As used in this specification and the appended claims, the singular of " a " and " an " also include Corresponding plural number, unless clearly there is other statements in text.In the context of the present invention, term " about " and " about " indicate this Skilled practitioner will be understood that the precision interval for still ensuring that the technical effect of the feature.The term usually show with it is shown Numerical value deviates ± 20%, preferably ± 15%, more preferably ± 10%, even more preferably ± 5%.It should be understood that term "comprising" is not It is restrictive.For the purpose of the present invention, term " by ... constitute " be considered as term " by ... constitute " preferred implementation side Case.If being hereinafter defined as the embodiment including at least certain amount for a certain group, this is intended to further include preferably only by this The group that a little embodiments are constituted.In addition, term " first " in the specification and in the claims, " second ", " third " or " (a) ", " (b) ", " (c) ", " (d) " etc. are used to distinguish similar to element and suitable not necessarily for description sequential order or time Sequence.It should be understood that interchangeable and invention described herein embodiment can in the appropriate case for the term so used It is operated with other sequences other than described herein or shown.Term " first ", " second ", " third " or " (a) ", " (b) ", In the case that " (c) ", " (d) ", " i ", " ii " etc. are related to the step of method or purposes or analysis, do not have between the steps Time or time interval coherence, i.e. these steps can carry out simultaneously or there may be several seconds, number between such step Divide, the time interval of a few hours, a couple of days, several weeks, several months or even several years, unless as above described below separately have finger in this application It is bright.It should be understood that the present invention is not limited to ad hoc approach as described herein, program, reagents etc., because these can change.Also answer What is understood is terms used herein merely to describing specific embodiment and being not intended to limit only by appended claims The scope of the invention of book limitation.Unless otherwise defined, it is usually that field is common that all technical and scientific terms used herein, which have, The identical meanings that technical staff is understood.

Term " nitrification inhibitor " is in this regard interpreted as slowing down or preventing the chemical substance of nitrifying process.Therefore, nitre Change inhibitor by inhibiting the activity of bacterium such as Nitromonas to delay Natural Transformation of the ammonium to nitrate anion.It is used herein Term " nitrification " is interpreted as ammonia (NH₃) or ammonium (NH₄ ⁺) by oxygen biological oxidation to nitrite anions (NO₂ ^-), then these nitrous Acid group is by microbiological oxidation at nitrate anion (NO₃ ^-).In addition to nitrate anion (NO₃ ^-) outside, nitrous oxide is also generated by nitrification.? In nitrogen cycle in soil, nitrification is important step.Therefore, inhibit nitrification that can also reduce N₂O loss.Term nitrification inhibits Agent is deemed to be equivalent to the compound and is inhibiting the purposes in nitrification.

Term " compound according to the present invention " or " compound of formula I " include that compound as defined herein and its solid are different Structure body, salt, tautomer or N- oxide.Term " the compounds of this invention " is interpreted as being equal to term " according to the present invention Compound ", therefore also include its stereoisomer, salt, tautomer or N- oxide.If it is of course understood that be in formula There is covering tautomer such as ketone-enol tautomers, imine-enamine tautomers, amide-imido in Compound I The substituent group of sour tautomer etc., then can there is only tautomers.In varied situations, term " compound of formula I " is no Including tautomer.If furthermore, it is to be understood that if there are at least one chiral centre or can be formed several in the molecule What isomers (cis/trans isomers), then only stereoisomer is possible.

Compound of formula I can be amorphous or can may have different macro properties such as to stablize with one or more Property or for example active different crystalline state (polymorph) of display different biological performance exist.The present invention relates to amorphous and crystallization formulas Compound I, the mixture of the different crystalline state of respective compound I and its amorphous or crystal salt.

The salt of compound of formula I preferably can agricultural salt.They can be formed in a usual manner, if such as compound of formula I tool If having basic functionality, by reacting the compound with the acid of the anion.Compound of formula I can agricultural salt especially wrap It includes its cation and anion those of not adversely affects sour acid-addition salts to the effect of compound of formula I respectively.Useful acid The anion of addition salts be mainly chloride ion, bromide ion, fluorine ion, bisulfate ion, sulfate radical, dihydrogen phosphate, hydrogen phosphate, Phosphate radical, nitrate anion, bicarbonate radical, carbonate, hexafluorosilicic acid root, hexafluoro-phosphate radical, benzoate anion and C₁-C₄Alkanoic acid Anion, preferably formate, acetate, propionate and butyric acid root.They can be by making compound of formula I and respective anionic Acid, preferably hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid reaction and formed.

Term " N- oxide " include it is any have at least one be oxidized to the tertiary N atom of N- oxide moieties Compound of formula I.Certainly, if nitrogen-atoms is present in compound of formula I, N- oxide can only be formed.

The organo moiety mentioned in the above-mentioned definition of each variable is the list of each group members as term halogen The collective term solely enumerated.Prefix C_n-C_mPossible carbon atom number in group is indicated in each case.

Term " halogen " indicates fluorine, bromine, chlorine or iodine, especially fluorine, chlorine or bromine in each case.

It is used herein and in alkyl amino, alkyl-carbonyl, alkylthio group, alkyl sulphinyl, alkyl sulphonyl and alcoxyl Term " alkyl " in the Alliyl moieties of base alkyl indicates usually there is 1-10 carbon atom in each case, often 1-6 carbon atom, preferably 1-4 carbon atom, the straight chain or branched-alkyl of more preferable 1-3 carbon atom.The example of alkyl is first Base, ethyl, n-propyl, isopropyl, normal-butyl, 2- butyl, isobutyl group, tert-butyl, n-pentyl, 1- methyl butyl, 2- methyl fourth Base, 3- methyl butyl, 2,2- dimethyl propyl, 1- ethyl propyl, n-hexyl, 1,1- dimethyl propyl, 1,2- dimethyl propyl, 1- methyl amyl, 2- methyl amyl, 3- methyl amyl, 4- methyl amyl, 1,1- dimethylbutyl, 1,2- dimethylbutyl, 1, 3- dimethylbutyl, 2,2- dimethylbutyl, 2,3- dimethylbutyl, 3,3- dimethylbutyl, 1- ethyl-butyl, 2- ethyl fourth Base, 1,1,2- thmethylpropyl, 1,2,2- thmethylpropyl, 1- ethyl -1- methyl-propyl and 1- Ethyl-2-Methyl propyl.

It is used herein and in halogenated alkyl carbonyl, haloalkoxycarbonyl, halogenated alkylthio, halogenated alkyl sulfonyl, halogen Term " halogenated alkyl " in the halogenated alkyl structure division of substituted alkyl sulfinyl, halogenated alkoxy and halogenated alkoxy alkyl Indicate that usually there is 1-10 carbon atom in each case, often 1-6 carbon atom, the straight chain of preferably 1-4 carbon atom Or branched-alkyl, wherein the hydrogen atom of the group is partially or completely substituted by halogen atom.Preferred halogenated alkyl structural portion sorting From C₁-C₄Halogenated alkyl, more preferable C₁-C₃Halogenated alkyl or C₁-C₂Halogenated alkyl, especially C₁-C₂Fluoroalkyl such as methyl fluoride, two Methyl fluoride, trifluoromethyl, 1- fluoro ethyl, 2- fluoro ethyl, 2,2- bis-fluoro ethyls, 2,2,2- trifluoroethyl, pentafluoroethyl group etc..

Terms used herein " alkoxy " indicates via oxygen atoms bond and usually there is 1-10 carbon in each case Atom, often 1-6 carbon atom, preferably 1-4 carbon atom, such as the straight chain or branched-alkyl of 1 or 2 carbon atom.Alcoxyl The example of base is methoxyl group, ethyoxyl, positive propoxy, isopropoxy, n-butoxy, 2- butoxy, isobutoxy, tert-butoxy Deng.

Terms used herein " alkoxyalkyl " is related to generally comprising 1-10, and usually from 1-4, preferably 1-2 carbon is former The alkyl of son, wherein 1 carbon atom has and generally comprises 1-4, the alkoxy as defined above of preferably 1 or 2 carbon atom. Example is CH₂OCH₃、CH₂-OC₂H₅, 2- methoxy ethyl and 2- ethoxyethyl group.

Terms used herein " alkylthio group " (alkyl sulfenyl: alkyl-S-), which refers to, has 1-10 via sulphur atom connection Carbon atom, preferably 1-4 carbon atom (=C₁-C₄Alkylthio group), the straight chain or branching saturated alkyl of more preferable 1-3 carbon atom.

Terms used herein " halogenated alkylthio " is related to alkylthio group as described above, wherein hydrogen moiety or completely quilt Fluorine, chlorine, bromine and/or iodine substitution.

Terms used herein " alkenyl " indicates usually there is 2-10 in each case, often 2-6, preferably 2- Single unsaturated alkyl of 4 carbon atoms, such as vinyl, allyl (2- propylene -1- base), 1- propylene -1- base, 2- propylene -2- Base, methylallyl (2- methyl propyl- 2- alkene-1- base), 2- butene-1-base, 3- butene-1-base, 2- amylene-1- base, 3- amylene- 1- base, 4- amylene -1- base, 1- methyl but-2-ene -1- base, 2- ethyl propyl- 2- alkene -1- base etc..

Terms used herein " alkenyloxy " indicates via oxygen atoms bond and usually there is 2-10 in each case, It is preferred that the alkenyl as defined above of 2-6 or 2-4 carbon atom.

Terms used herein " alkynyl " indicates usually there is 2-10 in each case, often 2-6, preferably 2-4 Single unsaturated alkyl of a carbon atom, such as acetenyl, propargyl (2- propine -1- base), 1- propine -1- base, 1- methyl propyl- 2- Alkynes -1- base, 2- butine -1- base, 3- butine -1- base, 1- pentyne -1- base, 3- pentyne -1- base, 4- pentyne -1- base, 1- methyl butyl- 2- alkynes -1- base, 1- ethyl propyl- 2- alkynes -1- base etc..

Terms used herein " alkynyloxy group " indicates via oxygen atoms bond and usually there is 2-10 in each case, excellent Select the alkenyl as defined above of 2-6 or 2-4 carbon atom.

Term " cycloalkyl-alkyl " is related to via alkyl, such as C₁-C₆Alkyl or C₁-C₄Alkyl, especially methyl (=cycloalkanes Ylmethyl) naphthenic base as defined above that is bonded with the rest part of the molecule.

Used herein and term " naphthenic base " in the cyclic alkyl moiety of cycloalkyloxy and cycloalkylthio is every The usually single ring alicyclic group with 3-10 or 3-6 carbon atom is indicated in the case of kind, such as cyclopropyl, cyclobutyl, ring penta Base, cyclohexyl, suberyl, cyclooctyl, cyclononyl and cyclodecyl or cyclopropyl, cyclobutyl, cyclopenta and cyclohexyl.

Used herein and term " cycloalkenyl " in the cycloalkenyl moiety of cyclenes oxygroup and cyclenes sulfenyl is every Indicate that usually there is 3-10, such as 3 or 4 or 5-10 carbon atom, the monocycle list insatiable hunger of preferably 3-8 carbon atom in the case of kind And nonaromatic.Exemplary cycloalkenyl groups include cyclopropanyl, cycloheptenyl or cyclo-octene base.

Term " cycloalkenyl alkyl " is related to the cyclenes as defined above being bonded via alkyl with the rest part of the molecule Base, such as C₁-C₆Alkyl or C₁-C₄Alkyl, especially methyl (=cycloalkenylmethyl).

Term " carbocyclic ring " or " carbocylic radical " are generally included comprising 3-12, preferably 3-8 or 5-8, more preferable 5 or 6 3-12 member of carbon atom, preferably 3-8 person or 5-8 member, more preferable 5 or 6 Yuans monocyclic non-aromatic rings.It is preferred that term " carbocyclic ring " cover as Naphthenic base defined in upper and cycloalkenyl.

Term " heterocycle " or " heterocycle " generally include 3-12 member, preferably 3-8 person or 5-8 member, more preferable 5 or 6 members, especially It is 6 Yuans monocyclic heterocycles nonaromatics.Heterocyclic non-aromatic group generally comprises 1,2,3,4 or 5, preferably 1,2 or 3 selected from N, The hetero atom of O and S is as ring members, wherein the S atom as ring members can be used as S, SO or SO₂In the presence of.5 or 6 element heterocycles The example of group includes saturation or unsaturated non-aromatic heterocyclic, as Oxyranyle, oxetanyl, Thietane base, Thietane base-S- oxide (S- oxo Thietane base), Thietane base-S- dioxide (S- dioxo sulphur Azetidinyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuran base, dihydrofuryl, 1,3- dioxolanyl, Tetrahydro-thienyl, S- oxo tetrahydro-thienyl, S- dioxotetrahydro thienyl, dihydrothiophene, S- oxo-dihydro thienyl, S- Dioxo dihydrothiophene,Oxazolidinyl,Oxazoline base, thiazolinyl, oxathiolane base, piperidyl, piperazinyl, pyrrole Mutter base, dihydro pyranyl, THP trtrahydropyranyl, 1,3- and 1,4- bis-Alkyl, thiapyran base, S- oxo thiapyran base, S- dioxo thiophene It mutters base, dihydro thiapyran base, S- oxo-dihydro thiapyran base, S- dioxo dihydro thiapyran base, tetrahydro thiapyran base, S- oxo tetrahydric thiapyran Base, S- dioxotetrahydro thiapyran base, morpholinyl, thio-morpholinyl, S- oxo thio-morpholinyl, S- dioxothiomorpholinyl, Thiazinyl etc..It include also pyrrolidin-2-one base, pyrrolidines -2,5- as the example of the heterocycle of ring members comprising 1 or 2 carbonyl Diketo, imidazolidin-2-one base,Oxazolidine-2- ketone group, thiazolidine -2 -one base etc..

Term " aryl " includes usually having 6-14, the monocyclic, bicyclic or tricyclic virtue of preferably 6,10 or 14 carbon atoms Race's group.Exemplary aryl includes phenyl, naphthalene and anthryl.It is preferred that phenyl is as aryl.

Term " heteroaryl " includes 5 or 6 Yuans lists comprising 1,2,3 or 4 hetero atom selected from N, O and S as ring members Ring heteroaromatic group.The example of 5 or 6 Yuans heteroaromatic groups includes pyridyl group, i.e. 2-, 3- or 4- pyridyl group, pyrimidine radicals, i.e. 2-, 4- or 5- pyrimidine radicals, pyrazinyl, pyridazinyl, i.e. 3- or 4- pyridazinyl, thienyl, i.e. 2- or 3- thienyl, furyl, i.e. 2- or 3- furyl, pyrrole radicals, i.e. 2- or 3- pyrrole radicals,Oxazolyl, i.e. 2-, 3- or 5-Oxazolyl, it is differentOxazolyl, i.e., 3-, 4- or 5- is differentOxazolyl, thiazolyl, i.e. 2-, 3- or 5- thiazolyl, isothiazolyl, i.e. 3-, 4- or 5- isothiazolyl, pyrazolyl, i.e., 1-, 3-, 4- or 5- pyrazolyl, imidazole radicals, i.e. 1-, 2-, 4- or 5- imidazole radicals,Di azoly, such as 2- or 5- [1,3,4] Di azoly, 4- or 5- (1,2,3-Diazole) base, 3- or 5- (1,2,4-Diazole) base, 2- or 5- (1,3,4- thiadiazoles) Base, thiadiazolyl group, such as 2- or 5- (1,3,4- thiadiazoles) base, 4- or 5- (1,2,3- thiadiazoles) base, 3- or 5- (1,2,4- thiophene Diazole) base, triazolyl, for example (,) 1H-, 2H- or 3H-1,2,3- triazole-4-yls, 2H- triazole -3- base, 1H-, 2H- or 4H-1,2, 4- triazolyl and tetrazole radical, i.e. 1H- or 2H- tetrazole radical.Term " heteroaryl " further includes comprising 1,2 or 3 selected from N, O and S Bicyclic 8-10 person heteroaromatic group of the hetero atom as ring members, wherein 5 or 6 Yuans heteroaromatic rings are condensed in benzyl ring or 5 or 6 members Heteroaromatic group.Condense in benzyl ring or 5 or 6 Yuans heteroaromatic groups 5 or the example of 6 Yuans heteroaromatic rings include benzofuranyl, Benzothienyl, indyl, indazolyl, benzimidazolyl, benzoThiazolyl, benzoDi azoly, diazosulfide base, BenzoPiperazine base, quinolyl, isoquinolyl, purine radicals, 1,8- phthalazinyl, pteridyl, pyrido [3,2-d] pyrimidine radicals Or pyridine-imidazole base etc..These condensed heteroaryls can be via any annular atom of 5 or 6 Yuans heteroaromatic rings or via condensed Rest part of the carbon atom bonding of phenyl moieties together in the molecule.

Term " benzyloxy " and " phenoxy group " relate separately to the benzyl being bonded via oxygen atom with the rest part of the molecule And phenyl.

Term " Heterocyclylalkyl " and " heteroaryl alkyl " are related separately to via C₁-C₆Alkyl or C₁-C₄Alkyl, especially first Heterocycle as defined above that base (difference=heterocyclyl methyl or hetervaromatic methyl) is bonded with the rest part of the molecule or Heteroaryl.

Term " aryl alkyl " is related to via C₁-C₆Alkyl or C₁-C₄Alkyl, especially methyl (=aryl methyl or phenyl Methyl) aryl as defined above that is bonded with the rest part of the molecule, example includes benzyl, 1- phenylethyl, 2- phenyl Ethyl etc..

Term " cyclic moieties " may relate to any be present in the compounds of this invention and cyclic annular as defined above Part, such as naphthenic base, cycloalkenyl, carbocyclic ring, Heterocyclylalkyl, heterocycloalkenyl, heterocycle, aryl, heteroaryl etc..

As detailed above, the present invention relates to the capsules comprising (1) core (a) and shell (b) or (2) matrix (c), wherein is selecting In the case where item (1), core (a) includes the benzyl propargyl ether compound of Formulas I and shell (b) includes shell material；And in option (2) In the case of, matrix (c) includes the benzyl propargyl ether compound and host material of Formulas I.

Compound of formula I is described in detail below.

It should be noted that compound of formula I is commercially available or can be prepared by means known in the art.Particularly, those of skill in the art Know that ether structure part can be by making suitable propargyl halide (such as propargyl bromide or propargyl chloride) and suitable benzyl Alcohol reacts or by reacting suitable propargyl ethanol come shape with suitable benzylic halides (such as benzyl bromide or benzyl chloride) At.About these synthetic routes, with reference to SU 1 773 901 A1 and N.B.Barhate (Indian Journal of Biochemistry&Biophysics, volume 39,2002, the 264-273 pages).

The preferred embodiment of each variable about compound of formula I limits below.

In one embodiment of the invention, compound of formula I has following general formula I:

Wherein

And wherein

Y is O or S；And

M is 0,1 or 2.

In a preferred embodiment of the compound of formula I as defined above, R¹For H and R²Selected from C₂-C₆Alkynes Base, C₂-C₆Alkynyloxy group, aryl-C₁-C₆Alkyl and heteroaryl-C₁-C₆Alkyl is preferably selected from C₂-C₄Alkynyl, C₂-C₄Alkynyloxy group, virtue Base-C₁-C₄Alkyl and heteroaryl-C₁-C₄Alkyl, most preferably heteroaryl-C₁-C₄Alkyl, especially triazolyl methyl.These chemical combination Object corresponds to Formulas I .a compound, wherein R²- a indicates to be selected from C₂-C₆Alkynyl, C₂-C₆Alkynyloxy group, aryl-C₁-C₆Alkyl and heteroaryl Base-C₁-C₆Alkyl is preferably selected from C₂-C₄Alkynyl, C₂-C₄Alkynyloxy group, aryl-C₁-C₄Alkyl and heteroaryl-C₁-C₄Alkyl, it is more excellent Choosing is selected from C₃Alkynyloxy group and heteroaryl-C₁-C₄Alkyl, most preferably heteroaryl-C₁-C₄The substitution of alkyl, especially triazolyl methyl Base.If R²- a is triazolyl methyl, then the preferably triazole structure part via one of nitrogen-atoms is bonded to methyl.Furthermore it is preferred that The triazole structure part is 1,2,4- triazole structure part.

In another preferred embodiment of the compound of formula I as defined above, R¹And R²Both for H.These are changed It closes object and corresponds to Formulas I .b compound:

In an embodiment of compound of formula I, A is phenyl, wherein the benzyl ring it is unsubstituted or have 1,2 Or 3 identical or different substituent Rs^A.Such compound corresponds to Formulas I .1 compound, (the R that wherein n is 0,1,2 or 3^A)_nTable Show the above-mentioned substitution possibility of the compound.

The compound that particularly preferred wherein n is 1 or 2, i.e. following compounds are I.1¹I.1²:

For compound as defined above, it should be understood that substituent R^AAny carbon that can reside in benzyl ring is former At son.

In preferred embodiments, the present invention relates to such as compounds of Formula I, wherein R¹For H, R²For R²- a and A are phenyl, Wherein the benzyl ring is unsubstituted or with 1,2 or 3 identical or different substituent R^A.Such compound is known as formula I.1.a compound, particularly preferred Formulas I .1¹.a compound and Formulas I .1².a compound.

In another preferred embodiment of the present, the present invention relates to such as compounds of Formula I, wherein R¹For H, R²It is phenyl for H, A, Wherein the benzyl ring is unsubstituted or with 1,2 or 3 identical or different substituent R^A.Such compound is known as formula I.1.b compound, particularly preferred Formulas I .1¹.b compound and Formulas I .1².b compound.

For compound as defined above, i.e. I.a, I.b, I.1, I.1¹, I.1², I.1.a, I.1¹.a, I.1².a, I.1.b, I.1¹.b, I.1².b, particularly preferred R^AIf present halogen, NO are then selected from₂、NR^cR^d、C₁-C₆Alkyl, C₁-C₆It is halogenated Alkyl, C₁-C₆Alkoxy, C₁-C₆Alkylthio group, phenoxy group and benzyloxy, wherein cyclic moieties can be unsubstituted or can To have 1 or 2 identical or different substituent R^a, wherein R^a、R^cAnd R^dIt is defined below:

R^aSelected from halogen, C₁-C₂Alkyl, C₁-C₂Alkoxy, or two substituent Rs on adjacent carbon atom^aCan be OCH₂CH₂O bridge or O (CH₂) O bridge；And

R^cAnd R^dIt is independently selected from H, C₁-C₄Alkyl and C₁-C₄Halogenated alkyl.

More preferable R^ASelected from halogen, NO₂、C₁-C₆Alkyl, C₁-C₆Halogenated alkyl, C₁-C₆Alkoxy and phenoxy group wherein should Phenoxy group can be unsubstituted or can have 1 or 2 identical or different substituent R^a, wherein R^aSelected from halogen.

More preferable R^ASelected from halogen, NO₂、C₁-C₂Alkyl, C₁-C₂Halogenated alkyl, C₁-C₂Alkoxy and phenoxy group wherein should Phenoxy group can be unsubstituted or can have 1 or 2 identical or different substituent R^a, wherein R^aSelected from halogen.

Most preferably R^ASelected from fluorine, chlorine, bromine, NO₂、CH₃、CF₃, methoxyl group and phenoxy group, wherein the phenoxy group can not taken In generation, can have 1 or 2 identical or different substituent R^a, wherein R^aSelected from fluorine, chlorine or bromine.

Therefore, the present invention is related to following compound of formula I in one embodiment, wherein

R¹And R²It is independently selected from H, C₂-C₆Alkynyl, C₂-C₆Alkynyloxy group, aryl-C₁-C₆Alkyl and heteroaryl-C₁-C₆ Alkyl, condition are R¹And R²In at least one be H, and wherein

A is phenyl, wherein the benzyl ring is unsubstituted or with 1,2 or 3 identical or different substituent R^A, In

R^ASelected from halogen, NO₂、NR^cR^d, C₁-C₆Alkyl, C₁-C₆Halogenated alkyl, C₁-C₆Alkoxy, C₁-C₆Alkylthio group, benzene oxygen Base and benzyloxy, wherein cyclic moieties can be unsubstituted or can have 1 or 2 identical or different substituent group R^a, wherein R^a、R^cAnd R^dIt is defined below:

Particularly, the present invention is related to Formulas I .1.a compound as defined above in a preferred embodiment, especially Formulas I .1¹.a or I.1².a compound, wherein R^ASelected from halogen, NO₂、C₁-C₆Alkyl, C₁-C₆Halogenated alkyl, C₁-C₆Alkoxy and Phenoxy group, wherein the phenoxy group can be unsubstituted or can have 1 or 2 identical or different substituent R^a, wherein R^aChoosing From halogen.

In an even more preferred embodiment, the present invention relates to Formulas I .1.a compounds as defined above, especially Formulas I .1¹.a Or I.1².a compound, wherein R^ASelected from halogen, NO₂、C₁-C₂Alkyl, C₁-C₂Halogenated alkyl, C₁-C₂Alkoxy and phenoxy group, In the phenoxy group can be unsubstituted or 1 or 2 identical or different substituent R can be had^a, wherein R^aSelected from halogen.

In even more preferably embodiment, the present invention relates to Formulas I .1.a compounds as defined above, especially formula I.1¹.a or I.1².a compound, wherein R^ASelected from fluorine, chlorine, bromine, NO₂、CH₃、CF₃, methoxyl group and phenoxy group, the wherein phenoxy group Can be unsubstituted or 1 or 2 identical or different substituent R can be had^a, wherein R^aSelected from fluorine, chlorine or bromine.

In addition, the present invention is related to Formulas I .1.b compound as defined above, especially formula in another preferred embodiment of the present I.1¹.b or I.1².b compound, wherein R^ASelected from halogen, NO₂、C₁-C₆Alkyl, C₁-C₆Halogenated alkyl, C₁-C₆Alkoxy and benzene Oxygroup, wherein the phenoxy group can be unsubstituted or can have 1 or 2 identical or different substituent R^a, wherein R^aIt is selected from Halogen.

In an even more preferred embodiment, the present invention relates to Formulas I .1.b compounds as defined above, especially Formulas I .1¹.b Or I.1².b compound, wherein R^ASelected from halogen, NO₂、C₁-C₂Alkyl, C₁-C₂Halogenated alkyl, C₁-C₂Alkoxy and phenoxy group, In the phenoxy group can be unsubstituted or 1 or 2 identical or different substituent R can be had^a, wherein R^aSelected from halogen.

In even more preferably embodiment, the present invention relates to Formulas I .1.b compounds as defined above, especially formula I.1¹.b or I.1².b compound, wherein R^ASelected from fluorine, chlorine, bromine, NO₂、CH₃、CF₃, methoxyl group and phenoxy group, the wherein phenoxy group Can be unsubstituted or 1 or 2 identical or different substituent R can be had^a, wherein R^aSelected from fluorine, chlorine or bromine.

Especially relevant is compound of formula I in the context of the present invention, wherein in the compound of formula I,

R¹And R²Respectively H,

R^ASelected from halogen, NO₂、NR^cR^d、C₁-C₆Alkyl, C₁-C₆Halogenated alkyl, C₁-C₆Alkoxy, C₁-C₆Alkylthio group, benzene oxygen Base and benzyloxy, wherein cyclic moieties can be unsubstituted or can have 1 or 2 identical or different substituent group R^a, in which:

R^aSelected from halogen, C₁-C₂Alkyl and C₁-C₂Alkoxy, or two substituent Rs on adjacent carbon atom^aIt can be with For OCH₂CH₂O bridge or O (CH₂) O bridge；

R^cAnd R^dIt is independently selected from H, C₁-C₄Alkyl and C₁-C₄Halogenated alkyl；

And wherein preferably

R^ASelected from halogen, NO₂、C₁-C₆Alkyl, C₁-C₆Halogenated alkyl, C₁-C₆Alkoxy, phenoxy group and benzyloxy, middle ring Shape structure division can be unsubstituted or can have 1 or 2 identical or different substituent R^a, in which:

R^aSelected from halogen, C₁-C₂Alkyl and C₁-C₂Alkoxy.

Particularly preferred compound of formula I, wherein in the compound of formula I, R¹And R²Respectively H；A is phenyl, wherein described Benzyl ring is unsubstituted or with 1,2 or 3 identical or different substituent R^A, wherein R^AIf present then selected from halogen, C₁-C₄Alkyl and C₁-C₄Alkoxy.

In particular it is preferred to the compound of formula I to collect in table 1 below.

Table 1

Especially relevant in the context of the present invention is to show with high-vapor-pressure but simultaneously as nitrification inhibitor Those of high activity compound of formula I.

In preferred embodiments, the vapour pressure of compound of formula I is more than more than 0.2Pa or even at 20 DEG C at 20 DEG C 1.0Pa。

In some embodiments, the vapour pressure of compound of formula I 0.2-4.0Pa at 20 DEG C, such as the 0.2- at 20 DEG C The 2.5Pa or 0.3-2.0Pa at 20 DEG C.In other embodiments, the vapour pressure of compound of formula I 0.5-4.0Pa at 20 DEG C, Such as the 0.5-2.5Pa or 0.6-2.0Pa at 20 DEG C at 20 DEG C.In other embodiments, the vapour pressure of compound of formula I exists 1.0-4.0Pa at 20 DEG C, such as the 1.0-2.5Pa or 1.2-2.0Pa at 20 DEG C at 20 DEG C.

Especially relevant is the compound of formula I with the 1.5-2.0Pa vapour pressure at 20 DEG C.

Vapour pressure can be measured by methods known in the art by thermogravimetric analysis.It in the context of the present invention, can be with Use the Mettler Toledo STAR thermogravimetric meter on glass plate with 5mg sample.As reference compound, 3 are especially measured, 4- dimethyl pyrazole (DMP), and measure the vapour pressure of the 3.7Pa at 20 DEG C.

Capsule according to the present invention hereinafter further specific definition.Particularly, to core shell capsule (option (1)) and Capsule (option (2)) based on matrix is explained in further detail.Firstly, detailed description core shell capsule.

In one embodiment, the present invention relates to the capsule comprising core (a) He shell (b), center (a) is wrapped by shell (b) Envelope, and wherein

Core (a) include such as claims defined in compound of formula I as defined above, and

Shell (b) includes shell material, is selected from:

(b1) polyaddition products of isocyanates；

(b2) poly- (methyl) acrylate；With

(b3) aminoplast.

Capsule can be prepared by method comprising the following steps: (1) miscella phase and water phase, wherein oil mutually includes Formulas I Object, optionally solvent and at least one lipophilicity monomer are closed, and wherein water phase optionally includes at least one monomer, and (2) make monomer oily mutually with water phase surface aggregate to form capsule of the present invention.

In addition to compound of formula I, capsule core optionally includes water immiscibility solvent (S).Preferably, solvent (S) is at 20 DEG C Under solubility in water be at most 20g/I, more preferably up to 5g/I, in particular up to 0.5g/I.In general, the boiling of solvent (S) Point is higher than 100 DEG C, preferably higher than 150 DEG C, is particularly above 180 DEG C (under 1 bars).

In this case, " solvent " it is uniformly mixed to mean that solvent (S) can be formed with compound of formula I as herein defined Close object or dissolution compound of formula I as herein defined.

It is preferred as solvent:

Aromatic hydrocarbon solvent, such as toluene, dimethylbenzene, tetrahydronaphthalene or alkylated naphthalene or derivatives thereof；

Aliphatic ester, such as C₁₀-C₂₂The C of fatty acid₁-C₁₀The methyl esters or ethyl ester of Arrcostab or vegetable oil, such as vegetable seed Oily methyl esters or corn oil methyl esters or glyceride such as vegetable oil, such as corn oil or rapeseed oil；Or

Fatty acid dialkyl amide, such as C₁₀-C₂₂The C of fatty acid₁-C₁₀Dialkyl amide.

The mixture of above-mentioned solvent is also possible.Water immiscibility solvent (S) is usually commercially available, such as trade name200、200 orAromatic hydrocarbon under 28.Aromatic hydrocarbon can be made with naphthalene depleted quality With.

The example of commercial sources of fatty acids ester be methyl oleate (such asES METI 05, Cognis, Germany).

The example of commercial sources of fatty acids dialkyl amide be octanoic acid, capric acid dimethylformamide (such as4296, Clariant, Germany) and dodecanoic acid.

Preferred solvent (S) is aromatic hydrocarbon as described above, aliphatic ester and fatty acid amide.

In one embodiment of the invention, preferably compound of formula I is with dissolved form, as suspension, lotion or outstanding Floating lotion is present in core (a).Preferably, compound of formula I exists with dissolved form.In addition, in this embodiment, core Chinese style The weight ratio of the sum of all solvents (such as solvent (S) and any cosolvent) is usually 5:1-1:10 in Compound I and core, preferably 3:1-1:2, more preferable 2:1-1:1.

Based on nuclear material total amount, the core (a) contains at least 10 weight %, preferably at least 30 weight %, particularly at least The compound of formula I of 50 weight %.Core (a) can contain at most 100 weight %, the preferably up to compound of formula I of 70 weight %.Core material The amount of material is usually summed it up by the amount of any solvent in compound of formula I and core.

Suitable shell material is known to those skilled in the art and includes:

(b1) polyaddition products of isocyanates, especially polyureas；

(b2) poly- (methyl) acrylate；Or

(b3) aminoplast, preferably condensate of melamine and formaldehyde.

The polyaddition products of preferred isocyanate.Particularly preferred polyureas.

The polyaddition products (b1) of preferred isocyanates can be obtained by the addition polymerization of following substance:

M1.1) at least one isocyanate derivates (M I) for being 30-100 weight % based on (b1),

M1.2) at least one amino-compound (M II) for being 0-70 weight % based on (b1), and/or

M1.3) at least one alcohol (M III) for being 0-70 weight % based on (b1).

Suitable isocyanate derivates (M I) are all isocyanic acids with two or more isocyanate groups Ester.For polyureas shell material, the isocyanates that is preferably listed below.

Suitable amino-compound (M II) is guanidine and its salt, diamines and polyamines and amino alcohol.It is preferred that diethylidene three Amine, N, bis- (3- aminopropyl) ethylenediamines of N'-, hexamethylene diamine (HMDA) and ethylenediamine (EDA).

Suitable alcohol (M III) is all two pure and mild polyalcohols.In addition, ethoxylation and propoxylation glycol and polyalcohol Properly.If the amount of M1.1 is 100 weight %, reaction is paired into water.

Addition polymerization process and relevant monomer (M I-M III) are for example described in US 4,021,595, EP 0 392 876 and EP In 0 535 384.

Particularly preferably with the capsule of the encapsulating material comprising polyureas, it is well known and can be similar to prior art system It is standby.They are preferably prepared by the interfacial polymerization method of suitable polymer shell forming material (such as polyisocyanates and polyamines). Interfacial polymerization is usually aqueous in the oil-in-water of the nuclear material comprising being dissolved at least part polymer shell forming material therein It is carried out in lotion or suspension.During polymerization, polymer is separated to the border surface between nuclear material and water from nuclear material, by This forms the shell of capsule.To obtain the aqueous suspension of capsule material.Suitable for preparing the glue containing agrochemical compound The method of the interfacial polymerization process of capsule has been disclosed in the prior art.

In general, polyureas is by making the polyisocyanates at least two isocyanate groups and having at least two primaquines The polyamines of base reacts to be formed, to form polyureas shell material.

In another embodiment, polyureas can be by forming polyisocyanates and water and contact.Preferably, polyurea shell Polyisocyanates and polyamines comprising polycondensation form.Suitable polyisocyanates is for example by the of 2010/0248963 A1 of US [0135]-[0158] section is it is known that with reference to entire contents.Suitable polyamines is for example by the of US 2010/0248963A1 [0159]-[0169] section is it is known that with reference to entire contents.

Polyisocyanates can be used alone or the mixture as two or more polyisocyanates uses.It is suitable more Isocyanates is such as aliphatic isocyanate or aromatic isocyanate.These isocyanates can be used as monomer or oligomeric isocyanide Acid esters exists.NCO content can be measured according to ASTM D 5155-96 A.

The example of suitable aliphatic diisocyanate includes tetramethylene diisocyanate, pentamethylene diisocyanate With the bis- isocyanates hexamethylenes of hexamethylene diisocyanate and alicyclic isocyanate such as isophorone diisocyanate, 1,4- Alkane and double-(4- isocyanates butylcyclohexyl) methane.

Suitable aromatic isocyanate includes toluene di-isocyanate(TDI) (mixture of TDI:2,4- and 2,6- isomers), two Phenylmethylene -4,4'- diisocyanate (MDI), polymethylene polyphenyl isocyanate, three isocyanide of 2,4,4'- diphenyl ether Acid esters, 3,3'- dimethyl -4,4'- diphenyl diisocyanate, 3,3'- dimethoxy-4 ', 4'- diphenyl diisocyanate, 1, 5- naphthalene diisocyanate and 4,4', 4 "-triphenyl methane isocyanates.The higher oligomers of above-mentioned diisocyanate are also Suitably, such as the isocyanuric acid ester of above-mentioned diisocyanate and biuret and its mixture with aforementioned diisocyanates.

In another preferred embodiment of the present, polyisocyanates is oligomeric isocyanates, preferably aromatic oligomeric isocyanates.This The oligomeric isocyanates of kind may include the above-mentioned aliphatic vulcabond and/or aromatic isocyanate of oli-gomeric forms.Oligomeric isocyanide The average functionality of acid esters is in the range of 2.0-4.0, preferably 2.1-3.2, more preferable 2.3-3.0.In general, these oligomeric isocyanides The viscosity (being measured according to DIN 53018) of acid esters is 20-1000mPas, more preferable 80-500mPas, especially 150- 320mPas.Such oligomeric isocyanates can be for example by BASF SE with trade nameM10、 M20、M50、M70、M200、MM103 or by Bayer Company withA270 is commercially available.

The adduct of suitable also diisocyanate and polyalcohol such as ethylene glycol, glycerol and trimethylolpropane, passes through Two corresponding to correspondent alcohol and its with the molal quantity of the hydroxyl value of the mixture of above-mentioned diisocyanate are added in every mole of polyol Isocyanates.In this way, the diisocyanate of several molecules is connected on polyalcohol by carbamate groups, with shape At the polyisocyanates of high molecular weight.Specially suitable this productL(Bayer Corp., It Pittsburgh) can be anti-with one mole of 2- ethyl glycerol (the bis- hydroxymethyl-propanes of 1,1-) by three moles of toluene diisocyanate It answers and prepares.Other suitable products pass through hexamethylene diisocyanate or isophorone diisocyanate and ethylene glycol or sweet Oily addition and obtain.

Preferred polyisocyanates is isophorone diisocyanate, diphenyl methane -4,4'- diisocyanate, toluene Diisocyanate and oligomeric isocyanates, wherein oligomeric isocyanates is particularly preferred.

Suitable polyamines in the scope of the invention will be appreciated that typically refer to those in the molecule to include two and more The compound of amino, these amino can be connect with aliphatic series or Aromatic moieties.

The example of suitable aliphatic polyamine is formula H₂N-(CH₂)_n-NH₂α, ω-diamines, wherein n is the integer of 2-6. The example of such diamines is ethylenediamine, propylidene -1,3- diamines, tetra-methylenedimine, five methylene diamine and hexa-methylene two Amine.Preferred diamines is hexamethylene diamine.Other suitable aliphatic polyamines are formula H₂N-(CH₂-CH₂-NH)_nThe polyethylene of-H Imines, wherein n is 2-20, preferably the integer of 3-5.The representative example of such polyethyleneimine is diethylenetriamines, Sanya Tetramine, tetren and penten.Other suitable aliphatic polyamines are dioxa alkane-α, ω-diamines, Such as formula H₂N-(CH₂)₃₀-(CH₂)₄O-(CH₂)₃-NH₂4,9- dioxa dodecane -1,12- diamines.

The example of suitable aromatic polyamine is 1,3- phenylenediamine, 2,4- and 2,6- toluenediamine, 4,4'- diamino-diphenyl Methane, 1,5- diaminonaphthalene, 1,3,5- triaminobenzene, 2,4,6- triaminotoluene, 1,3,6- triamido naphthalene, tri- ammonia of 2,4,4'- Yl diphenyl ether, 3,4,5- triamido -1,2,4- triazole and 1,4,5,8- tetra-amino anthraquinone.Those are not soluble in water or have in water The polyamines of deficiency dissolution can be used as the use of its hydrochloride.

Polyamines, such as those described above can be used alone or the mixture as two or more polyamines uses.It is preferred that Polyamines be polyethyleneimine, such as tetren.

The hull shape of each complementation will change at the relative quantity of component with its equivalent.Generally, it is preferred to the amount of about stoichiometry, And a kind of excessive component also can be used, especially excessive polyisocyanates.Hull shape is approximately corresponding at the total amount of component The total amount of polymer shell forming material.

Preferred poly- (methyl) acrylate (b2) can be obtained by the polymerization of following monomer:

M2.1 acrylic acid C) is selected from based on at least one that (b2) is 30-100 weight %₁-C₂₄Arrcostab, methacrylic acid C₁-C₂₄Arrcostab, acrylic acid, methacrylic acid, methacrylic anhydride and methacrylonitrile monomer (M IV)；

M2.2) at least one monomer (M V) selected from polyfunctional monomer for being 0-70 weight % based on (b2)；With

M2.3 monomer (M IV) and (M V)) are structurally different from based on at least one that (b2) is 0-40 weight % Other monomers (M VI).

As monomer (M IV), preferably acrylic acid and methacrylic acid C₁-C₂₄Arrcostab and methacrylonitrile.It is preferred that Monomer (M IV) is methyl acrylate, ethyl acrylate, n-propyl, isopropyl acrylate, n-butyl acrylate, propylene Sour isobutyl ester, sec-butyl acrylate and tert-butyl acrylate and stearyl acrylate base ester and methyl methacrylate, methyl-prop Olefin(e) acid ethyl ester, n propyl methacrylate, isopropyl methacrylate, n-BMA, Isobutyl methacrylate, The mixture of the secondary butyl ester of methacrylic acid, Tert-butyl Methacrylate and methacrylonitrile and above-mentioned monomer.

In above-mentioned monomer, preferred methacrylate.Particularly preferred methyl acrylate, ethyl acrylate, acrylic acid are different Propyl ester, n-butyl acrylate and tert-butyl acrylate and methyl methacrylate, ethyl methacrylate, methacrylic acid are different Propyl ester, n-BMA, Tert-butyl Methacrylate and stearyl acrylate base ester.Particularly preferred methyl methacrylate Ester, n-butyl acrylate and stearyl acrylate base ester.

Suitable monomer (M V) is polyfunctional monomer, in water slightly soluble (if any), but is had in lipophilic substance Have good to limited dissolubility.The microsolubility of monomer (M V) is understood to mean that under 20 DEG C and 1013 millibars in water Solubility < 60g/I.

In the context of the present invention, polyfunctional monomer is understood to mean that the list at least two unconjugated double bonds Body.Preferred polyfunctional monomer is divinyl or polyvinyl monomer；The ester of glycol or polyalcohol and acrylic acid；Glycol is more The ester of first alcohol and methacrylic acid；The ether and glycol of glycol or polyalcohol and allyl alcohol or the ether of polyalcohol and vinyl alcohol.

Particularly preferred tool is 1,2- glycol diacrylate, 1,3- third there are two the monomer (M V) of unconjugated double bond Omega-diol diacrylate, 1,4 butanediol diacrylate, 1,5 pentandiol diacrylate and 1,6-HD diacrylate Ester, 1,2- ethylene glycol dimethacrylate, 1,3- dimethacrylate, 1,4- butanediol dimethacrylate Ester, 1,5- dimethacrylate and 1,6-HD dimethylacrylate, divinylbenzene, ethylene glycol dimethyl Acrylate, 1,3 butylene glycol dimethylacrylate, methallyl butylmethacrylamide and allyl methacrylate. Very particularly preferably 1,3- propylene glycol diacrylate, 1,4 butanediol diacrylate, 1,5 pentandiol diacrylate and 1,6 hexanediol diacrylate, 1,3- dimethacrylate, 1,4- butanediol dimethylacrylate, 1,5- penta Diol dimethacrylate and 1,6-HD dimethylacrylate.

It is particularly preferred have greater than two unconjugated double bonds monomer (M V) be trimethylolpropane trimethacrylate, Trimethylol-propane trimethacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate and pentaerythrite four Acrylate and its mixture.

Suitable monomer (M VI) is monomer lIla), such as butadiene, isoprene, vinyl acetate, vinyl propionate And vinylpyridine and lllb) water-soluble monomer, such as acrylonitrile, Methacrylamide, acrylic acid, methacrylic acid, clothing Health acid, maleic acid, maleic anhydride, n-vinyl pyrrolidone, 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate and Acrylamide-2-methylpro panesulfonic acid, N hydroxymethyl acrylamide, N- methylol methacrylamide, dimethylaminoethyl acrylate methyl Amino-ethyl ester and methacrylic acid diethyllaminoethyl ester.What is be particularly suitable is N hydroxymethyl acrylamide, N- methylol first Base acrylamide, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate.Particularly preferably mentioned at M IV And acrylate free acid, i.e. acrylic acid, especially methacrylic acid.

M2.1 methyl acrylate, ethyl acrylate, acrylic acid) are selected from based on at least one that (b2) is 30-100 weight % Isopropyl ester, n-butyl acrylate and tert-butyl acrylate and methyl methacrylate, ethyl methacrylate, methacrylic acid Isopropyl ester, n-BMA, Tert-butyl Methacrylate and stearyl acrylate base ester monomer (M IV)；

M2.2 butanediol diacrylate, trimethylolpropane) are selected from based on at least one that (b2) is 0-70 weight % Triacrylate, trimethylol-propane trimethacrylate, pentaerythritol triallyl ether, pentaerythritol triacrylate and The monomer (M V) of pentaerythritol tetraacrylate；With

M2.3) the acrylic acid and/or methacrylic acid for being 0-40 weight % based on (b2).

Particularly preferred poly- (methyl) acrylate (b2) can be obtained by the polymerization of following monomer:

M2.1 methyl methacrylate, stearyl acrylate base) are selected from based on at least one that (b2) is 30-100 weight % The monomer (M IV) of ester and n-butyl acrylate；

M2.3) the acrylic or methacrylic acid for being 0-40 weight % based on (b2).

Poly- (methyl) acrylate (b2) can be obtained by the procedure known to those skilled in the art, for example, by In the absence of solvent, in the solution, in dispersions or in lotion free radical, anion or cationic polymerization.Preferably be selected from by Base polymerization.Particularly preferred aqueous free-radical emulsion polymerization, suspension polymerisation and aqueous free radical micro-emulsion polymerization.

In particularly preferred embodiments, it is 1-50 weight that polymer beads, which include in each case based on (b2), % is measured, preferably the methacrylic acid of the amount of 1-20 weight % is as component M2.3 (M VI).

Preferred condensate of melamine and formaldehyde (b3) can be obtained by the polycondensation of following substance:

M3.1) melamino-formaldehyde prepolymer (M VII)；And/or

M3.2) the alkyl ether (M VIII) of melamino-formaldehyde prepolymer.

Polymer (b3) can be obtained by known polycondensation reaction known to those skilled in the art.Melamino-formaldehyde The preparation of resin and capsule is for example described in EP 0 974 394, US 4,172,119, EP-A 0 026 914 and EP-A 0 In 218 887.

In view of above-mentioned, in one embodiment of the invention, preferred capsule, wherein shell material is selected from

(b1) polyaddition products of isocyanates, it includes:

(b1a) at least one polyfunctional isocyanate of polymerized form and at least one polyfunctional amine；Or

(b1b) at least one polyfunctional isocyanate of polymerized form and at least one polyfunctional alcohol；Or

(b1c) more at least one polyfunctional isocyanate of polymerized form and at least one polyfunctional amine and at least one Functional alcohol.

Particularly preferred polyureas is as shell material.

In another embodiment of the present invention, preferred capsule, wherein shell material be

(b2a) poly- (methyl) acrylate comprising methyl methacrylate and/or methacrylic acid in polymerized form； Or

(b3a) aminoplast comprising melamine and formaldehyde in polymerized form.

About (b2a), "and/or" means that poly- (methyl) acrylate may include the methyl methacrylate in polymerized form Or the combination of methacrylic acid or both.

In the capsule comprising core (a) and shell (b), center (a) is encapsulated by shell (b), and wherein

Shell (b) includes shell material, is selected from:

(b1) polyaddition products of isocyanates；

(b2) poly- (methyl) acrylate；With

(b3) aminoplast,

The weight ratio of its center (a) and shell (b) can be 50:50-99:1.

In preferred embodiments, the weight ratio of core (a) and shell (b) is 70:30-98:2, preferably 75:25-95:5.

Those of skill in the art know, for the releasing properties of capsule, core shell weight ratio is important feature.Depending on shell (presence (see below the explanation of offer) and the granularity of capsule for optionally including protecting colloid (see below this respect to material Further details), it may be necessary to adjust core shell weight ratio to obtain certain required characteristics.

Preferred shell material, the granularity of capsule and core shell weight ratio are adjusted according to the present invention, so that 1 at 20-25 DEG C After it, at most the 65% of discharge active component total amount, preferably up to 50%, more preferably up to 30 weight %.It is preferred that at 20-25 DEG C After lower 3 days, there are still at least 10 weight % of active constituent total amount, more preferably at least 20 weight % in capsule, more preferably at least 30 weight %.

The invention further relates to a kind of methods for preparing capsule of the present invention, comprising the following steps:

A) compound of formula I, optionally water immiscibility solvent, water and encapsulation agent are mixed,

B) nonionic or cationic surfactant or protecting colloid is added as emulsifier,

C) by emulsifying mixture, and

D) other encapsulation agents are optionally added into and polymerize encapsulation agent to form capsule.

The surfactant for being suitable as emulsifier is nonionic and cationic surfactant.It is preferred that non-ionic surface is living Property agent.

Suitable nonionic surfactant is alcoxylates, and N- is alkylated fatty acid amide, amine oxide, ester or sugar Based surfactants.The example of alcoxylates be such as alkoxylated alcohol, alkyl phenol, amine (such as butter fat Amine), amide, aryl phenol, fatty acid or aliphatic ester compound.Ethylene oxide and/or propylene oxide can be used for alkoxy Change, preferably ethylene oxide.The example that N- is alkylated fatty acid amide is fatty acid glucamides or Marlamid.Ester Example be aliphatic ester, glyceride or monoglyceride.The example of glycosyl surfactant active is that anhydro sorbitol, ethoxylation are de- Water sorbierite, sucrose and glucose ester or alkyl polyglucoside.The example of suitable cation surfactant is that season surface is living Property agent, such as the salt of the quaternary ammonium compound with one or two hydrophobic group or long chain primary amines.Particularly preferred nonionic table Face activating agent, wherein hydrophobic part is made of alkyl, aralkyl, propylene oxide or butylene oxide, and hydrophilic segment is by oxidation second Alkene or ethylene oxide/propylene oxide unit composition.

Details in relation to protecting colloid are provided below.

Monomer polymerization can be caused by heating.Properly, polymerization can be controlled by additionally increasing temperature, institute The polymer of generation forms capsule shells, surrounds capsule core.The rule is for example described at WO 03/0166050 page 7 17 rows clearly quote the content of the document into the eighth row of page 8.In general, in the course of the polymerization process, the energy ratio of introducing emulsifies It is few in the process.Preferably, for this purpose, reducing mixing speed and/or using another type of blender.

In the case where being based on the capsule of poly- (methyl) acrylate, list can also be caused by the way that polymerization initiator is added Body polymerization.Suitable initiator is known in the art.Initiator can reside in both water phase and continuous phase.

In general, being aggregated in 20-150 DEG C, carried out at a temperature of preferably 40-120 DEG C, especially 60-95 DEG C.Preferably, add Heat gradually carries out.

Advantageously, polymerization carries out under standard pressure.However, it is carried out under can also boosting in decompression or slightly, such as Under the polymerization temperature greater than 100 DEG C, therefore about in the range of 0.5-10 bars.

Polymerization reaction time is generally 1-10 hours, usually 2-5 hours or 1-3 hours.

In general, capsule can be prepared in the presence of at least one organic or inorganic protecting colloid.

Therefore, in one embodiment of the invention, the shell (b) of capsule includes organic or inorganic protecting colloid.

Organic and inorganic protecting colloid can be ion or neutrality.In this regard, protecting colloid both can individually make With, it is possible to have the mixture of several protecting colloids of identical or different charge uses.

Preferred organic protecting colloid is water-soluble polymer.Particularly preferred organic protecting colloid, by the surface of water Power is reduced to 45-70mN/m from maximum 73mN/m, to promote the formation of closed capsule shell, and forms the glue with preferred size Capsule.

Neutral organic protecting colloid is, for example, cellulose derivative, for example, hydroxyethyl cellulose, methyl hydroxyethylcellulose, Methylcellulose and carboxymethyl cellulose, polyvinylpyrrolidone, vinylpyrrolidone copolymer, gelatin, Arabic gum, Xanthan gum, casein, polyethylene glycol, polyvinyl alcohol and the polyvinyl acetate of partial hydrolysis and methylhydroxypropylcellulose.

Polyvinyl alcohol can be prepared by the following: make vinyl acetate poly- in the presence of comonomer if appropriate It closes, and makes polyvinyl acetate ester hydrolysis, wherein acetyl group breaks to form hydroxyl.The degree of hydrolysis of polymer for example can be 1- 100%, preferably 50-100%, specifically for 65-95%.Term " polyvinyl acetate of partial hydrolysis " is in present patent application The degree of hydrolysis less than 50% is understood as referring in context, term " polyvinyl alcohol " is understood as referring at least hydrolysis of 50-100% Degree.

It is preferred that polyvinyl alcohol or the polyvinyl acetate of partial hydrolysis, the viscosity of the aqueous solution of 4 weight % is at 20 DEG C The value of 3-56mPas, the preferably value of 14-45mPas are shown according to DIN 53015.It is preferred that having at least 65%, preferably extremely Few 70%, the polyvinyl alcohol of especially at least 75% degree of hydrolysis.

The organic protecting colloid of anion is such as mosanom, polymethylacrylic acid and its copolymer and sulfoethyl Ethyl ester, sulfoethyl methacrylate, sulfopropyl acrylate, methacrylic acid sulphopropyl, N- (sulfoethvl) Malaysia acyl Imines, 2- acrylamido -2- alkyl sulfonic acid, styrene sulfonic acid and vinyl sulfonic acid copolymer.Preferred anion is organic Protecting colloid polyacrylic acid and phenolsulfonic acid/formaldehyde condensation products for naphthalene sulfonic acids and naphthalene sulfonic acids/formaldehyde condensation products and specifically.

As inorganic protecting colloid, it can be mentioned that " Pickering system ", which makes it possible to consolidate by very thin Body particle is stabilized, and insoluble but dispersible in water, or insoluble and non-dispersible in water but can pass through lipophilic Property substance wetting.

In this regard, Pickering system can improve the particle in water by individual solid particle or in addition The auxiliary agent composition that dispersibility or the particle pass through the wettability of lipophilicity phase.

Inorganic solid particle can be metal salt, such as salt, the oxidation of calcium, magnesium, iron, zinc, nickel, titanium, aluminium, silicon, barium or manganese Object and hydroxide.It can be mentioned that magnesium hydroxide, magnesium carbonate, magnesia, calcium oxalate, calcium carbonate, barium carbonate, barium sulfate, dioxy Change titanium, aluminium oxide, aluminium hydroxide and zinc sulphide.Equally it can be mentioned that silicate, bentonite, hydroxyapatite and hydrotalcite.It is special Silica, magnesium pyrophosphate or the tricalcium phosphate of not preferred high degree of dispersion.

The silica of high degree of dispersion can be used as fine solid particles and be dispersed in water.It is referred to as dioxy however, also can be used The aqueous colloidal dispersion (being also described as silica solution) of SiClx in water.This kind of aqueous colloidal dispersion is the alkaline aqueous mixing of silica Object.In alkaline pH range, particle is swollen in water and stablizes.To using these dispersions as Pickering system and Speech, it is advantageous that the pH of oil-in-water emulsion is adjusted to the pH of 2-7 with acid.

According to an embodiment, preferably inorganic protecting colloid and its mixture with organic protecting colloid.

According to other embodiments, preferably neutral organic protecting colloid.It is preferred that having the protecting colloid of OH group, such as poly- Vinyl alcohol, the polyvinyl acetate of partial hydrolysis and methylhydroxypropylcellulose.Particularly preferred at least two neutral protecting colloids, The mixture of the especially at least two kinds protecting colloids with OH group.Very particularly preferably polyvinyl alcohol and methylhydroxypropyl are fine Tie up the mixture of element.

In general, it is 0.1-15 weight %, preferably 0.5-10 weight % that the dosage of protecting colloid, which is based on water phase,.To inorganic protection For colloid, being preferably selected in this regard based on water phase is 0.1-15 weight %, the preferably mixture of 0.5-10 weight %.

It is preferred that water phase of the amount of organic protecting colloid based on lotion is 0.1-15 weight %, preferably 0.5-10 weight %.Root According to specific embodiment, preferably 0.1-15 weight %, the organic protecting colloid of neutrality of preferably 0.5-10 weight %.It is special in this regard The protecting colloid with OH group of not preferred 0.1-15 weight %, preferably 0.5-10 weight %, such as polyvinyl alcohol, part water The polyvinyl acetate and methylhydroxypropylcellulose of solution.

In this regard, preparation method and selected one or more protecting colloids are depended on, can equally be the component of capsule. Therefore, the at most 20 weight % of the total weight based on capsule can be protecting colloid.According to the embodiment, capsule is in polymer Surface on show as one or more protecting colloids.

According to the present invention, certain combinations of shell material and protecting colloid may be preferred.For example, polyurea shell can be by poly- Vinyl alcohol is stablized as protecting colloid or by Pickering stabilisation.Similarly, polyacrylate shell can pass through polyethylene Alcohol is stablized as protecting colloid or by Pickering stabilisation.

As described above, the present invention is directed not only to core shell capsule (scheme (1)), and it is related to the capsule (scheme based on matrix (2)).Capsule based on matrix is hereinafter described in further detail.

Therefore, in another embodiment, the present invention relates to the capsule comprising matrix (c), mesostromas

(c) comprising, with compound of formula I as defined above and host material, being selected as defined in claims From:

(c1) poly- (methyl) acrylate；With

(c2) calcium alginate.

Therefore, host material can be poly- (methyl) acrylate or calcium alginate.

Poly- (methyl) acrylate (c2) for matrix can be as described above just poly- (methyl) propylene as shell material Same monomer for acid esters (b2) obtains.

Calcium alginate (c1) can be by with CaCl₂Solidify solution of sodium alginate to obtain.For example, the calcium alginate glue of compound of formula I Capsule can be by emulsifying the compound of formula I of 20 weight % and in CaCl in 2% solution of sodium alginate₂Solidification mixture in solution It obtains.The mass median particle size of gained bead is usually 3-5mm, can be used for direct fertilizer mixing.Alternatively, 300 μm can be prepared Or smaller beads and as suspension apply.It can also realize other granularities defined below.

Activity component concentration in matrix capsule can change in a wide range.Based on matrix total amount, it is preferable that matrix (c) Contain at least compound of formula I of 10 weight %.Matrix (c) can contain at most 95 weight %, the preferably up to Formulas I of 70 weight % Close object.

In general, core shell capsule and the capsule based on matrix all can be used as capsule offer, it is suitable for direct fertilizer and mixes, or It is provided as microcapsules, such as in the form of capsule suspension liquid.

Therefore, in one embodiment, capsule according to the present invention has following mass median particle size:

It is greater than 300 μm, preferably 1mm or bigger, more preferable 1-6mm, even more preferably 3-5mm；Or

- 300 μm or smaller, preferably 50nm-200 μm, more preferable 0.5-50 μm.

If capsule has greater than 300 μm, preferably 1mm or bigger mass median particle size, they are especially suitable for direct Application.

If capsule has 300 μm or smaller mass median particle size, they are especially suitable for capsule suspension liquid (CS) Form application.

Mass median particle size can be by determination of laser diffraction, this is the mature skill that ISO13320 (2009) is covered Art.Details in relation to laser diffraction also provide in CIPAC MT187 (CIPAC handbook K).

In the case where microcapsules, D50 is preferably 0.5-80 μm, more preferable 1.0-50 μm, even more preferably 2.0-10.0 μ M, most preferably 2.0-8.0 μm；And D90 is preferably 1.0-145 μm, more preferable 2.0-60 μm, even more preferably 4.0-20 μm, most It is preferred that 6.0-15.0 μm.

It is preferred that the following combination of D50 and D90 value: D50:0.5-80 μm, D90:1.0-145 μm, preferably D50:1.0-50 μm, D90:2.0-60 μm, more preferable D50:2.0-10.0 μm, D90:4.0-20 μm, most preferably D50:2.0-8.0 μm, D90:6.0- 15.0μm。

The present invention also provides the Aquo-compositions comprising capsule according to the present invention.Aquo-composition usually contains 5-80 weight Measure %, the preferably capsule of 10-60 weight %.Aquo-composition usually contains at least 2 weight %, preferably at least 5 weight %, especially It is the encapsulating compound of formula I of at least 8 weight %.Aquo-composition is usually contained less than 79.2 weight %, preferably smaller than 59.4 weights Measure the compound of formula I of %.Preferably, Aquo-composition includes 2-79.2 weight %, preferably 5-75 weight %, more preferable 8-59.4 The compound of formula I of weight %.

In general, composition includes 0.5-25 weight %, preferably 1.0-20 weight %, the especially surface 2.0-15 weight % are living Property substance.Preferred surface reactive material is those of outlined above.

Aquo-composition according to the present invention can also include the adjuvant for the chemicals preparaton that is often used in agriculture.It is used auxiliary Auxiliary agent is respectively depending on specific application form and active material.The example of suitable adjuvant be dispersing agent or emulsifier (such as other Solubilizer, protecting colloid, surfactant and adhesive), organic and inorganic thickening agent, fungicide, antifreezing agent, defoaming agent, conjunction There are also colorants and tackifier or adhesive (such as seed treatment formulation) if suitable.

Suitable surface reactive material (adjuvant, wetting agent, tackifier, dispersing agent or emulsifier) is preferably outlined above Those of.

Thickener (assigns composition with modified mobility, i.e., in the high viscosity and agitation under quiescent conditions The compound of low viscosity) example be polysaccharide and organic and inorganic clay, as Xanthan Gum (CP Kelco, USA),23 (French Rhodia),(R.T.Vanderbilt, USA) or(Engelhard Corp., NJ, USA).Fungicide can be added to save and stablize the composition.Properly kill The example of microbial inoculum is based on those of antiphen and benzyl alcohol hemiformal (ICIOr Thor ChemieRS's and Rohm&Haas) and isothiazolinone derivatives such as alkyl isothiazole quinoline ketone MK Class and benzoisothiazolinone class be (Thor Chemie'sMBS).The example of Suitable antifreeze agents is ethylene glycol, third Glycol, urea and glycerol.The example of defoaming agent be polysiloxane emulsion (such asSRE, German Wacker orFrench Rhodia), long-chain alcohol, fatty acid, fatty acid salt, organofluorine compound and its mixture.Tackifier Or the example of adhesive be polyvinylpyrrolidone, polyvinyl acetate, polyvinyl alcohol and cellulose ether (Japan Shin-Etsu)。

Present invention also contemplates that the non-aqueous composition comprising capsule of the present invention, about activity component concentration, surface-active substance Matter and the above-mentioned preferred situation of adjuvant are also applicable.Oil can be used mutually to replace water phase, to obtain oil dispersion.

Suspended phase (including the phase of capsule of the present invention) is suitable than being 1:0.5-1 with liquid phase (such as water phase or oily phase): 100, more preferable 1:1-1:10.

Preferably there is 300 μm or smaller mass median particle size for the capsule in capsule suspension liquid as defined above, And commonly referred to as microcapsules.

In view of above-mentioned, the present invention is related to a kind of capsule suspension liquid in one embodiment, it includes:

It include the suspended phase of capsule as herein defined, wherein the mass median particle size of capsule is 1mm or smaller, excellent Select 300 μm or smaller；With

Liquid phase；

Wherein the ratio between suspended phase and liquid phase are preferably 1:0.5-1:100, more preferable 1:1-1:10.

Preferably, the ratio can be 1:1-1:7, such as 1:1-1:4.

In preferred embodiments, surface reactive material and/or adjuvant as defined above can in addition be deposited.

Liquid phase can be oily phase or water phase.Preferably, which is water phase.

Since capsule of the present invention includes to show active compound of formula I as nitrification inhibitor, capsule of the present invention or Capsule suspension liquid is advantageously used in the mixture comprising fertilizer and capsule of the present invention or capsule suspension liquid.Alternatively, capsule or Capsule suspension liquid can be used in the mixture with carrier, then, for example, fertilizer or and Fertilizer Combination can be applied to.

In addition, capsule of the present invention, capsule suspension liquid and mixture are advantageously used for agriculture application, especially inhibit nitrification The purpose of effect.Particularly, they are beneficial for long period of activity.

In one embodiment, the present invention relates to a kind of mixture, it includes:

(ii) capsule according to the present invention or capsule suspension liquid.

Preferred situation about the mixture comprising fertilizer defines in further detail below.

If mixture includes inorganic or organic carrier particle as component (i), the mixture is preferably applied to fertilizer Or and Fertilizer Combination.Inorganic carrier preferably includes clay, attapulgite, bentonite base carrier.Organic carrier preferably includes fiber Plain paper pulp base carrier.

In general, inorganic and organic carrier (hereinafter referred to as carrier) includes solid carrier such as plant gel or hydrogel, Or mine soil, such as silicate, silica gel, talcum, kaolin, lime stone, lime, chalk, bole, loess, clay, white clouds Stone, diatomite, calcium sulfate, magnesium sulfate, magnesia；The synthetic material ground, fertilizer, such as solid or liquid, inorganic fertilizer containing ammonium is such as NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or ammonium phosphate；Solid or liquid organic fertilizer such as liquid fertilizer, Semiliquid fertilizer, barnyard manure, biogas manure and compost made of stalks, compost from earthworm, compost, seaweed or guano, or containing urea fertilizer as urinated Element, anhydrous ammonia, urea ammonium nitrate (UAN) solution, urea sulphur, stabilizes urea, urea base NPK fertilizer or urea sulphur at urea formadehyde The product of sour ammonium and plant origin, such as flour, bark powder, wood powder and shuck powder, cellulose powder and other solid carriers. Other suitable examples of carrier include fumed silica or precipitated silica, they for example can be used as glidant, resistive connection Block agent, grinding aid are for being used for liquid actives in solid formulations and as carrier.The additional examples of suitable carrier It is microparticle, such as is adhered to plant leaf and discharges the microparticle of its content within a certain period of time.In specific embodiment In, the plural gel microparticle that agriculture chemistry carrier such as can be used to convey plant protecting activity ingredient can be used, such as such as Described in US6,180,141；Or comprising at least one vegetable active compound and encapsulating auxiliary agent composition, wherein the auxiliary agent include Fungal cell or its segment, such as described in WO 2005/102045；Or it is coated with the carrier of lipophilicity tackifier on the surface Grain, wherein carrier granular is attached to the surface of plant, dogstail and weeds, such as disclosed in US 2007/0280981.At other In specific embodiment, such carrier may include special strong bonding molecule, ensure that the carrier is adhered to plant, seed And/or wherein plant growth or be intended to grow place, until its content conveys completely.For example, the carrier can be or Comprising Cellulose-binding Domain of Microbiological (CBD), useful reagent that the latter is described as connecting molecular species with cellulose (see US 6, 124,117)；Or the direct fusion between CBD and enzyme；Or can be used for conveying the multi-functional fusion protein of encapsulated reagent, In multi-functional fusion protein can by for carbohydrate combined area the first combined area and the second combined area constitute, wherein first Combined area or the second combined area (can also see WO 03/031477) in conjunction with microparticle.Other suitable examples of carrier include by The bifunctional fusion proteins that CBD and the anti-RR6 antibody fragment in conjunction with microparticle are constituted, the complex can be deposited on tread Or (WO 03/031477 is also seen) on the grass cut off.In another embodiment, which can be carrier for active principle Particle, the latter are applied using the wetting activity for example including gum arabic, guar gum, karaya, bassora gum and locust bean gum Layer is attached to the surface of such as plant, dogstail, weeds, seed and/or wherein plant growth or the place for being intended to grow etc..It is inciting somebody to action When particle of the present invention is applied on plant surface, carrys out autoprecipitation, irrigation, dew, particle is used in conjunction with by special application equipment Water, or the discharge water from plant itself can be attached to the enough moisture of plant surface offer to the particle and (also see US 2007/0280981)。

In another embodiment, which can be polyaminoacid or may include polyaminoacid.Poly- amino Acid can be obtained according to any suitable method, such as by polymerizeing one or more single amino acid, such as glycine, alanine, figured silk fabrics Propylhomoserin, leucine, isoleucine, phenylalanine, proline, tryptophan, serine, tyrosine, cysteine, methionine, day Asparagine, glutamine, threonine, aspartic acid, glutamic acid, lysine, arginine, histidine and/or ornithine.Poly- ammonia Base acid can combine with nitrification inhibitor of the present invention and in some embodiments can also be with other load as described above Body or other nitrification inhibitors as described herein are combined with any proper ratio.For example, polyaminoacid can be with the present invention Nitrification inhibitor is combined with ratio of the 1-10 (polyaminoacid) to 0.5-2 (nitrification inhibitor of the present invention).

In one embodiment, the present invention relates to capsule according to the present invention or capsule suspension liquids or mixture in agricultural Purposes in Chemical activator, wherein the purposes preferably includes to apply capsule according to the present invention or capsule suspension liquid or mixture For the root zone of plant, soil, soil substitute and/or wherein plant growth or be intended to grow place.

Preferably, purposes is for reducing nitrification.

In one embodiment, the present invention relates to a kind of methods for reducing nitrification, including by capsule according to the present invention Or capsule suspension liquid or mixture are applied to the root zone of plant, soil, soil substitute and/or wherein plant growth or are intended to raw Long place.

Preferably to the root zone of plant, soil, soil substitute and/or wherein plant growth for such use or method Or the place for being intended to grow is additionally provided fertilizer, wherein capsule according to the present invention or capsule suspension liquid or mixture and fertilizer Application can carry out simultaneously or with certain time lag progress, preferably by most 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.

For mixture and such use of the invention or method, fertilizer includes:

Solid or liquid inorganic fertilizer containing ammonium, preferably NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or Ammonium phosphate；

Solid or liquid organic fertilizer, preferred liquid fertilizer, semiliquid fertilizer, biogas manure, barnyard manure and compost made of stalks, earthworm Muck, compost, seaweed or guano；Or

Containing urea fertilizer such as urea, urea formadehyde, urea ammonium nitrate (UAN) solution, urea sulphur, stabilize urea, urea base NPK fertilizer or urea ammonium sulfate.

Other preferred situations about purposes of the present invention, method and mixture are defined below.

It can be based on for capsule according to the present invention or capsule suspension liquid or mixture being applied in accordance with the purpose of the invention The plant that is grown on soil and/or wherein plant growth or the place for being intended to grow or the purposes can be based on by bases Capsule or capsule suspension liquid of the invention or mixture are applied to wherein plant growth or the soil for being intended to grow or soil substitution Object.In a particular embodiment, capsule according to the present invention or capsule suspension liquid or mixture can be used in the case where plant is not present It nitrifies in reducing, such as the warming-up exercise of subsequent rural activity, or is used in other industrialized regions unrelated with agricultural Nitrification is reduced, such as environment, water conservation, power generation or similar purpose.In a particular embodiment, capsule according to the present invention Or capsule suspension liquid or mixture can be used for reducing nitrification in sewage, mud, fertilizer or animal wastes such as pig or cow dung.Example Such as, capsule according to the present invention or capsule suspension liquid or mixture can be used in sewage treatment plant, biogas plant, cowshed, liquid Nitrification is reduced in fertilizer tank or container etc..In other embodiments, capsule according to the present invention or capsule suspension liquid or mixing Object can be used in animal, such as reduce nitrification on the spot in productivity livestock.It therefore, can be by capsule according to the present invention Or capsule suspension liquid or mixture are fed for animal, such as mammal, such as together with suitable feed, and thus in animal Lead to the reduction of nitrification in gastrointestinal tract, this causes the discharge from gastrointestinal tract to reduce again.The activity is fed according to the present invention Capsule or capsule suspension liquid or mixture can be repeated once to multiple, such as every 2nd day, the 3rd day, the 4th day, the 5th day, the 6th It, the 7th day, perhaps weekly, every 2 weeks, every 3 weeks or monthly, every 2 months etc..

The purposes, which may further include, is applied to capsule according to the present invention or capsule suspension liquid or mixture wherein Nitrification occurs or assumes or be expected the environment, area or the region that nitrify.The environment, area or region can not include planting Object or soil.For example, capsule according to the present invention or capsule suspension liquid or mixture can be used for the nitre in laboratory environment Change and inhibit, such as reaction etc. is urged based on enzyme.It further include the purposes in greenhouse or similar indoor equipment.

Terms used herein " reducing nitrification " or " reduction of nitrification " are related to being slowed or shut off for nitrifying process, such as pass through Delay or eliminate Natural Transformation of the ammonium to nitrate anion.The reduction can be that apply capsule or capsule according to the present invention wherein outstanding The complete or partial elimination nitrified at the plant or place of supernatant liquid or mixture.For example, partially remove may cause on plant or In plant residual nitrification, or wherein plant growth or be intended to grow soil soil substitute in or residual nitre thereon Change with wherein without using capsule according to the present invention or capsule suspension liquid or mixture compare situation be comparably about 90% to 1%, such as 90%, 85%, 80%, 70%, 60%, 50%, 40%, 30%, 20%, 10% or less than 10%, for example, 5% or Less than 5%.In certain embodiments, partially removing may cause on plant or in plant or wherein plant growth or is intended to Residual in the soil or soil substitute of growth or thereon is nitrified and is wherein hanged without using capsule according to the present invention or capsule The control situation of supernatant liquid or mixture is compared less than 1%, and for example, 0.5%, 0.1% or lower.

The purposes of capsule according to the present invention or capsule suspension liquid or mixture in reduction nitrification can be single use, Or it can be reuse.It, can be by the nitrification inhibitor or correspondent composition only with physiologically related as single use Time interval be supplied to its target position, such as soil or place or object, such as plant is primary, such as 1 year one Secondary perhaps every 2-5 it is primary or during the service life of plant it is primary.

In other embodiments, which can be repeated at least once more each time cycle, for example, can will according to this The capsule or capsule suspension liquid or mixture of invention are at its target position or object between the time of a couple of days, several weeks or several months Every it is interior for reducing nitrification twice.It is used herein above and below capsule according to the present invention or capsule suspension liquid or the purposes of mixture Term " at least once " refers to that capsule according to the present invention or capsule suspension liquid or mixture can be used twice, or several times, It can include repeating or being repeated several times application or processing.The repetition can be 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 It is secondary, frequently reuse for 10 times or more times.

Terms used herein " irrigation " be related to irrigating plant or in which plant growth or be intended to grow place or soil or Soil substitute, wherein described pour includes mentioning capsule according to the present invention or capsule suspension liquid or mixture together with water For.

Capsule according to the present invention or capsule suspension liquid or mixture can further include added ingredient, for example, at least one Kind agricultural chemical compound.For example, capsule according to the present invention or capsule suspension liquid or mixture can be removed additionally comprising at least one Careless compound and/or at least one Fungicidal compounds and/or at least one Pesticidal compound and/or at least one nematicide And/or at least one biological pesticide and/or at least one bioenergizer.

In other embodiments, capsule according to the present invention or capsule suspension liquid or mixture can further include one Kind or a variety of replacements or additional nitrification inhibitor.The example of the replacement that may include or additional nitrification inhibitor is sub- oil Acid, alpha-linolenic acid, p-Coumaric Acid methyl esters, Ferulic acid methylester, 3- (4- hydroxy phenyl) methyl propionate (MHPP), karanjin, Brachialacton, 1,4-benzoquinone sorgoleone, 2- chloro- 6- (trichloromethyl) pyridine (N-Serve or N-serve), dicyandiamide (DCD, DIDIN), 3,4- dimethyl pyrazole phosphate (DMPP, ENTEC), 2- (3,4- dimethyl -1H- pyrazol-1-yl) amber Acid or 2- (4,5- dimethyl -1H- pyrazol-1-yl) succinic acid (DMPSA), 3,4- dimethyl pyrazoleGlycol hydrochlorate (DMGA), 3,4- dimethyl pyrazoleCitrate (DMPC), 3,4- dimethyl pyrazoleLactate (DMPL), 3,4- dimethyl pyrazoleThe chloro- 3- methylpyrazole (CIMP) of mandelate (DMPM), 1,2,4- triazole, 4-, 4- amino -1,2,4- triazole hydrochloride (ATC), the chloro- 6- methylpyrimidine (AM) of 1- amide groups -2- thiocarbamide (ASU), 2- amino -4-, 2-mercaptobenzothiazole (MBT), 5- Ethyoxyl -3- trichloromethyl -1,2,4- thiadiazoles (kobam (terrazole), etridiazole), 2- sulphathiazole (ST), ATS (Ammonium thiosulphate) (ATU), 3- methylpyrazole (3-MP), 3,5- dimethyl pyrazole (DMP), 1,2,4- triazole urea (TU), N- (1H- Pyrazolmethyl) ethanamide such as N- ((3 (5)-methyl-1 H- pyrazol-1-yl) methyl) acetamide and N- (1H- pyrazolyl first Base) benzamide type such as N- ((3 (5)-methyl-1 H- pyrazol-1-yl) methylformamide, (chloro- 3 (5) 4--methylpyrazole -1- base N- Methyl) formamide, dicyandiamide, urea with formaldehyde reacts adduct (such as WO 2011/137393 A1 or US2016/0060184 Described in A1), N- (3 (5), 4- dimethyl pyrazole -1- ylmethyl) formamide, China tree (neem), based on China tree (neem) at Product, the cyanamide, melamine, zeolite powder, catechol, benzoquinones, sodium tetraborate (sodium terta board), zinc sulfate divided.

In other embodiments, capsule according to the present invention or capsule suspension liquid or mixture can further include one kind Or a variety of urease inhibitors.The example for the urease inhibitor that may include include N- N-(n-butyl) thiophosphoric triamide (NBPT, Agrotain), N- n-propyl thiophosphoric acid triamide (NPPT), 2- nitrobenzophenone phosphoric triamide (2-NPT), those of skill in the art The mixing of other known NXPT, phenyl phosphorus diamides acid esters (PPD/PPDA), quinhydrones, ATS (Ammonium thiosulphate) and NBPT and NPPT Object (such as seeing US 8,075,659).Such of NBPT and NPPT mixture may include 40-95 based on the total amount of active material Weight %, the preferably NBPT of 60-80 weight %.Such mixture is sold as LIMUS, to include about 16.9 weight % The composition of the other compositions of NBPT, about 5.6 weight %NPPT and about 77.5 weight % including solvent and auxiliary agent.

In other embodiments, capsule according to the present invention or capsule suspension liquid or mixture can further include one kind Or various plants growth regulator.The example for the plant growth regulator that may include is anti-auxin, auximone, cell point Split element, defoliant, ethylene modulators, ethylene evolution agent, gibberellin class, growth inhibitor, morphactin, growth retardant, growth Stimulin and unassorted plant growth regulator.

Suitable example to anti-auxin used according to the invention is clofibric acid or 2,3,5 triiodobenzoic acid.

Suitable example to auximone used according to the invention is 4-CPA, 2,4-D, 2,4-DB, 2,4-DEP, 2, 4- drop propionic acid (dichlorprop), 2,4,5- tears propionic acid (fenoprop), IAA (indole-3-acetic acid), IBA, naphthaleneacetamide, α- Methyl α-naphthyl acetate, 1- naphthols, naphthoxy acetic acid, cyclic potassium naphthenate, sodium naphthenate or 2,4,5-T.

Suitable example to the basic element of cell division used according to the invention is 2iP, 6-benzyl aminopurine (6-BA) (=N-6- Benzyladenine), 2,6- lutidines (N- oxide -2,6- lutidine), 2,6- lutidines, kinetin or corn Element.

Suitable example to defoliant used according to the invention is Aero cyanamid, dimethipin (dimethipin), dichlobenil (endothal), merphos (merphos), metoxuron (metoxuron), pentachlorophenol (pentachlorophenol), match two Azoles element (thidiazuron), De-Green (tribufos) or three tributyl thiophosphates.

Suitable example to ethylene modulators used according to the invention be Ai Wei hormone, 1- methyl cyclopropene (1-MCP), Adjust naphthenic acid (prohexadione) (Prohexadione calcium) or TrinexAN_SNacethyl (trinexapac) (Trinexapac-ethyl).

Suitable example to ethylene evolution agent used according to the invention is ACC, silicon long element (etacelasil), ethephon (CEPHA),2-(chloroethyl) phosphonic acid (ethephon) or glyoxime (glyoxime).

Suitable example to gibberellin class used according to the invention is gibberellin or gibberellic acid.

Suitable example to growth inhibitor used according to the invention is that abscisic acid (abscisic acid), S- fall off Acid, ancymidol (ancymidol), Amex820 (butralin), first how prestige (carbaryl), chlorination(chlorphonium)、 Chlorpropham (chlorpropham), dikegulac (dikegulac), maleic Min (flumetralin), fluoridamid (fluoridamid), phosphine ammonium element (fosamine), glyphosine (glyphosine), the phonetic propyl alcohol of benzene (isopyrimol), jasmine Acid, maleic hydrazide (maleic hydrazide), mepiquat chloride (mepiquat) (helping strong element, five boric acid mepiquat chlorides), the dilute element of piperazine (piproctanyl), jasmine propyl propionate (prohydrojasmon), Chem hoe (propham) or 2,3,5 triiodobenzoic acid.

Suitable example to morphactin used according to the invention is chlorine fluorenic acid (chlorfluren), chloroflurenol (chlorflurenol), dichloro hydroxyl fluorenic acid (dichlorflurenol) or Florencol (flurenol).

Suitable example to growth retardant used according to the invention is that chlormequat (chlormequat) is (short Strong element), daminozide (daminozide), flurprimidol (flurprimidol), fluorine grass sulphur (mefluidide), paclobutrazol (paclobutrazol), cyclenes (tetcyclacis), uniconazole P (uniconazole), penta azoles bacterium (metconazol) of ring are adjusted.

Suitable example to growth stimulant used according to the invention is brassinosteroid (brassinolide), adjusts pyrrole Urea (forchlorfenuron) or hydroxyisoxazole (hymexazol).

Suitable example to unassorted plant growth regulator used according to the invention is alachlor (amidochlor), fluorine sulfanilamide (SN) careless (benzofluor), special gram grass (buminafos), carvol (carvone), choline chloride, Benzene cyanogen butyramide (ciobutide), benzene pyridazone acid (clofencet), cloxyfonac (cloxyfonac), cyanamide, cyclanilide (cyclanilide), cycloheximide (cycloheximide), cyprosulfamide, epocholeone, Ethychlozate, ethylene, pyridazine ketone acid (fenridazon), fluprimidol, careless fluorine (fluthiacet), heptopargil are reached (heptopargil), chloroethene sulfinic acid (holosulf), inabenfide (inabenfide), karetazan, lead arsenate, methasulfocarb (methasulfocarb), than reaching agriculture (pydanon), sintofen, difluoro pyrrole grand (diflufenzopyr) or triapenthenol (triapenthenol)。

In preferred embodiments, capsule according to the present invention or capsule suspension liquid or mixture may include Formulas I chemical combination The combination of the nitrification inhibitor of object and at least one compound selected from the group comprising following component: abscisic acid, alachlor, pyrimidine Alcohol, 6-benzyl aminopurine (=N-6- benzyladenine), brassinosteroid, Amex820, chlormequat (cycocel), chlorination Choline, cyclanilide, daminozide, difluoro pyrrole be grand, dikegulac, dimethipin, 2,6- lutidines, ethephon (CEPHA),2-(chloroethyl) phosphonic acid, maleic Min, tune Phonetic alcohol reaches careless fluorine, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, fluorine grass sulphur, mepiquat chloride (helping strong element), 1- Methyl cyclopropene (1-MCP), N-6- benzyladenine, paclobutrazol, adjusts naphthenic acid (Prohexadione calcium), jasmine propyl propionate, match at methyl α-naphthyl acetate Diazole element, triapenthenol, three tributyl thiophosphates, 2,3,5 triiodobenzoic acid, TrinexAN_SNacethyl and uniconazole P.

In other embodiments, capsule according to the present invention or capsule suspension liquid or mixture can further include one Kind or Multiple Pesticides.

Pesticide is usually chemistry or biological reagent (such as pesticide activity component, compound, composition, virus, bacterium, antibacterial Agent or disinfectant), nuisance is prevented by its effect, disability, kills or baffles in other respects.Objective pests can wrap Include destroy property, cause trouble, spread the disease or the insect for disease vector, phytopathogen, weeds, mollusk, Birds, mammal, fish, nematode (roundworm) and microorganism.Term " pesticide " further includes the expected growth for changing plant, blooms Or the plant growth regulator of reproduction rate；The defoliant for causing leaf or other leaves to fall off from plant, this generally promotes harvest； Promote living tissue, such as dry desiccant of undesirable aboveground vegetation part；Activation plant physiology function is to defend certain to have The plant activator of evil object；Pesticide is reduced to the safener for being not intended to herbicide effect of crops；And influence plant physiology machine The plant of any other mass parameter of plant growth, biomass, yield or the yielding of crops product can for example be enhanced Growth promoter.

The following pesticide I (such as pesticidal active substance) that compound I can be used therewith is used to illustrate possible group It closes, but does not limit them:

A) respiration inhibitor

The complex III inhibitor (such as strobilurins class) in the site-Qo: nitrile Fluoxastrobin (azoxystrobin) (A.1.1), first fragrant bacterium ester (coumethoxystrobin) (A.1.2), coumoxystrobin (coumoxystrobin) (A.1.3), ether Bacterium amine (dimoxystrobin) (A.1.4), Enestroburin (enestroburin) (A.1.5), alkene oxime amine (fenaminstrobin) (A.1.6), fenoxystrobin/ fluorine bacterium mite ester (flufenoxystrobin) (A.1.7), fluorine it is phonetic Bacterium ester (fluoxastrobin) (A.1.8), imines bacterium (kresoxim-methyl) (A.1.9), mandestrobin (A.1.10), pitch phenalgin amide (metominostrobin) (A.1.11), orysastrobin (orysastrobin) (A.1.12), ZEN 90160 (picoxystrobin) (A.1.13), pyraclostrobin (pyraclostrobin) (A.1.14), Pyrametostrobin (A.1.15), pyraoxystrobin (pyraoxystrobin) (A.1.16), trifloxystrobin (trifloxystrobin) (A.1.17), 2- (2- (3- (2,6- dichlorophenyl) -1- methyl acrol aminooxymethyl) benzene Base) -2- methoxyimino-N- methylacetamide (A.1.18), pyribencarb (A.1.19), triclopyricarb/ chlorodincarb(A.1.20)、Famoxadone (famoxadone) (A.1.21), Fenamidone (fenamidone) (A.1.21), N- [2- [(Isosorbide-5-Nitrae-dimethyl -5- Phenylpyrazole -3- base) oxygroup methyl] phenyl]-N- methoxy carbamate first Ester (A.1.22), 1- [the chloro- 2- of 3- [[1- (4- chlorphenyl) -1H- pyrazole-3-yl] oxygroup methyl] phenyl] -4- methyl tetrazolium -5- Ketone (A.1.23), 1- [the bromo- 2- of 3- [[1- (4- chlorphenyl) pyrazole-3-yl] oxygroup methyl] phenyl] -4- methyl tetrazolium -5- ketone (A.1.24), 1- [2- [[1- (4- chlorphenyl) pyrazole-3-yl] oxygroup methyl] -3- aminomethyl phenyl] -4- methyl tetrazolium -5- ketone (A.1.25), 1- [2- [[1- (4- chlorphenyl) pyrazole-3-yl] oxygroup methyl] -3- fluorophenyl] -4- methyl tetrazolium -5- ketone (A.1.26), 1- [2- [[1- (2,4- dichlorophenyl) pyrazole-3-yl] oxygroup methyl] -3- fluorophenyl] -4- methyl tetrazolium -5- ketone (A.1.27), 1- [2- [[4- (4- chlorphenyl) thiazol-2-yl] oxygroup methyl] -3- aminomethyl phenyl] -4- methyl tetrazolium -5- ketone (A.1.28), 1- [the chloro- 2- of 3- [[4- (p-methylphenyl) thiazol-2-yl] oxygroup methyl] phenyl] -4- methyl tetrazolium -5- ketone (A.1.29), 1- [3- cyclopropyl -2- [[2- methyl -4- (1- methylpyrazole -3- base) phenoxy group] methyl] phenyl] -4- methyl four Azoles -5- ketone (A.1.30), 1- [3- difluoro-methoxy -2- [[2- methyl -4- (1- methylpyrazole -3- base) phenoxy group] methyl] benzene Base] -4- methyl tetrazolium -5- ketone (A.1.31), 1- methyl -4- [3- methyl -2- [[2- methyl -4- (1- methylpyrazole -3- base) benzene Oxygroup] methyl] phenyl] tetrazolium -5- ketone (A.1.32), 1- methyl -4- [3- methyl-the 2- [[Asia 1- [3- trifluoromethyl] second Amino] oxygroup methyl] phenyl] tetrazolium -5- ketone (A.1.33), (Z, 2E) -5- [1- (2,4- dichlorophenyl) pyrazole-3-yl] oxygen Base -2- methoxyimino-N, 3- dimethyl-penten -3- enamine (A.1.34), (Z, 2E) -5- [1- (4- chlorphenyl) pyrazole-3-yl] Oxygroup -2- methoxyimino-N, 3- dimethyl-penten -3- enamine (A.1.35), (Z, 2E) -5- [1- (the chloro- 2- fluorophenyl of 4-) pyrrole Azoles -3- base] oxygroup -2- methoxyimino-N, 3- dimethyl-penten -3- enamine (A.1.36)；

The complex III inhibitor in the site-Qi: cyazofamid (cyazofamid) (A.2.1), amisulbrom (A.2.2), 2 Methylpropionic acid [(3S, 6S, 7R, 8R) -8- benzyl -3- [(3- acetoxyl group -4-methoxypyridine -2- carbonyl) amino] -6- first Base -4,9- dioxo -1,5- dioxy nonyl ring -7- base] ester (A.2.3), 2 Methylpropionic acid [(3S, 6S, 7R, 8R) -8- benzyl -3- [[3- acetoxymethoxy -4-methoxypyridine -2- carbonyl] amino] -6- methyl -4,9- dioxo -1,5- dioxy nonyl ring - 7- yl] ester (A.2.4), 2 Methylpropionic acid [(3S, 6S, 7R, 8R) -8- benzyl -3- [(3- isobutoxy carbonyloxy group -4- methoxyl group Pyridine -2- carbonyl) amino] -6- methyl -4,9- dioxo -1,5- dioxy nonyl ring -7- base] ester (A.2.5), 2 Methylpropionic acid [(3S, 6S, 7R, 8R) -8- benzyl -3- [[3- (1,3- benzodioxole -5- ylmethoxy) -4-methoxypyridine - 2- carbonyl] amino] -6- methyl -4,9- dioxo -1,5- dioxy nonyl ring -7- base] ester (A.2.6)；2 Methylpropionic acid (3S, 6S, 7R, 8R) -3- [[(3- hydroxyl -4- methoxyl group -2- pyridyl group) carbonyl] amino] -6- methyl -4,9- dioxo -8- (phenyl first Base) -1,5- dioxy nonyl ring -7- base ester (A.2.7), isobutyric acid (3S, 6S, 7R, 8R) -8- benzyl -3- [3- [(isobutyl acyloxy) Methoxyl group] -4-methoxypyridine amide groups] -6- methyl -4,9- dioxo -1,5- dioxy nonyl ring -7- base ester (A.2.8)；

Complex II inhibitor (such as carboxyl acylamide): benodanil (benodanil) (A.3.1), Benzovindiflupyr (A.3.2), bixafen (A.3.3), Boscalid (boscalid) (A.3.4), carboxin (carboxin) (A.3.5), methuroxam (fenfuram) (A.3.6), fluopyram (fluopyram) (A.3.7), flutolanil (flutolanil) (A.3.8), fluxapyroxad (fluxapyroxad) (A.3.9), furan pyrazoles it is clever (furametpyr) (A.3.10), isofetamid (A.3.11), isopyrazam (A.3.12), the third oxygen mebenil (mepronil) (A.3.13), Oxycarboxin (oxycarboxin) (A.3.14), penflufen (A.3.14), pyrrole metsulfovax (penthiopyrad) (A.3.15), sedaxane (A.3.16), tecloftalam (tecloftalam) (A.3.17), thifluzamide (thifluzamide) (A.3.18), N- (4'- trifluoromethylthio biphenyl -2- base) -3- difluoromethyl -1- methyl-1 H- pyrazole-4-carboxamide (A.3.19), N- (2- (1,3,3- trimethyl butyl) phenyl) the fluoro- 1H- pyrazole-4-carboxamide of -1,3- dimethyl -5- (A.3.20), 3- (difluoromethyl) -1- methyl-N- (1,1,3- trimethyl -2,3- dihydroindene -4- base) pyrazole-4-carboxamide (A.3.21), 3- (trifluoromethyl) -1- methyl-N- (1,1,3- trimethyl -2,3- dihydroindene -4- base) pyrazole-4-carboxamide (A.3.22), 1,3- dimethyl-N-(1,1,3- trimethyl -2,3- dihydroindene -4- base) pyrazole-4-carboxamide (A.3.23), 3- (trifluoromethyl) -1,5- dimethyl-N-(1,1,3- trimethyl -2,3- dihydroindene -4- base) pyrazole-4-carboxamide (A.3.24), 1,3,5- trimethyl-N- (1,1,3- trimethyl -2,3- dihydroindene -4- base) pyrazole-4-carboxamide (A.3.25), N- (the fluoro- 1,1,3- trimethyl -2,3- dihydroindene -4- base of 7-) -1,3- Dimethyl-pyrazol -4- formamide (A.3.26), N- [2- (2,4 dichloro benzene base) -2- methoxyl group -1- Methylethyl] -3- (difluoromethyl) -1- methyl pyrazole -4- Formamide (A.3.27)；

Other respiration inhibitors (such as complex I, agent of uncoupling): difluoro woods (diflumetorim) (A.4.1), (5,8- Difluoro quinazoline -4- base)-{ 2- [the fluoro- 4- of 2- (4- trifluoromethyl pyridine -2- base oxygroup) phenyl] ethyl } amine (A.4.2)；Nitro Phenyl derivatives: binapacryl (binapacryl) (A.4.3), dinobuton (dinobuton) (A.4.4), dinocap (dinocap) (A.4.5), fluazinam (fluazinam) (A.4.6)；Ferimzone (ferimzone) (A.4.7)；Organo-metallic compound: triphen Tinbase salt, such as fentinacetate (fentin-acetate) (A.4.8), Fentin chloride (fentin chloride) (A.4.9) or toadstool Tin (fentin hydroxide) (A.4.10)；ametoctradin(A.4.11)；And Silthiopham (silthiofam) (A.4.12)；

B) sterol biosynthesis inhibitor (SBI fungicide)

- C14 demethylase inhibitors (DMI fungicide): triazole type: penta ring azoles (azaconazole) (B.1.1), double Benzotriazole alcohol (bitertanol) (B.1.2), bromuconazole (bromuconazole) (B.1.3), cyproconazole (cyproconazole)(B.1.4)、Ether azoles (difenoconazole) (B.1.5), olefin conversion (diniconazole) (B.1.6), olefin conversion M (diniconazole-M) (B.1.7), oxole bacterium (epoxiconazole) (B.1.8), benzoxazole (fenbuconazole) (B.1.9), Fluquinconazole (fluquinconazole) (B.1.10), Flusilazole (flusilazole) (B.1.11), Flutriafol (flutriafol) (B.1.12), hexaconazole (hexaconazole) (B.1.13), amide azoles (imibenconazole) (B.1.14), cycltebuconazole (ipconazole) (B.1.15), penta azoles bacterium (metconazole) of ring (B.1.17), nitrile bacterium azoles (myclobutanil) (B.1.18), oxpoconazole (B.1.19), paclobutrazol (paclobutrazole) (B.1.20), penconazole (penconazole) (B.1.21), propiconazole (propiconazole) (B.1.22), prothioconazoles (prothioconazole) (B.1.23), simeconazoles (simeconazole) (B.1.24), penta azoles Alcohol (tebuconazole) (B.1.25), fluorine ether azoles (tetraconazole) (B.1.26), triazolone (triadimefon) (B.1.27), triadimenol (triadimenol) (B.1.28), triticonazole (triticonazole) (B.1.29), uniconazole P (uniconazole)(B.1.30),1-[rel-(2S；3R) -3- (2- chlorphenyl) -2- (2,4 difluorobenzene base) Oxyranyle Methyl] -5- thiocyano -1H- [1,2,4] triazole (B.1.31), 2- [rel- (2S；3R) -3- (2- chlorphenyl) -2- (2,4- difluoro Phenyl) oxiranylmethyl radical] -2H- [1,2,4] triazole -3- mercaptan (B.1.32), 2- [the chloro- 4- of 2- (4- chlorophenoxy) benzene Base] the amyl- 2- alcohol (B.1.33) of -1- (1,2,4- triazol-1-yl), 1- [4- (4- chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- Cyclopropyl -2- (1,2,4- triazol-1-yl) ethyl alcohol (B.1.34), 2- [4- (4- chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1,2,4- triazol-1-yl) butyl- 2- alcohol (B.1.35), 2- [the chloro- 4- of 2- (4- chlorophenoxy) phenyl] -1- (1,2,4- triazole -1- Base) butyl- 2- alcohol (B.1.36), 2- [4- (4- chlorophenoxy)-2- (trifluoromethyl) phenyl]-3- methyl-1-(1,2,4- triazole- 1- yl) butyl- 2- alcohol (B.1.37), 2- [4- (4- chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1,2,4- triazol-1-yl) Propan-2-ol (B.1.38), 2- [the chloro- 4- of 2- (4- chlorophenoxy) phenyl]-3- methyl-1-(1,2,4- triazol-1-yl) butyl- 2- alcohol (B.1.39), 2- [4- (4- chlorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1,2,4- triazol-1-yl) amyl- 2- alcohol (B.1.40), 2- [4- (4- fluorophenoxy) -2- (trifluoromethyl) phenyl] -1- (1,2,4- triazol-1-yl) propan-2-ol (B.1.41), 2- [the chloro- 4- of 2- (4- chlorophenoxy) phenyl] the amyl- 3- alkynes -2- alcohol (B.1.51) of -1- (1,2,4- triazol-1-yl)； Imidazoles: imazalil (imazalil) (B.1.42), pefurazoate (pefurazoate) (B.1.43), Prochloraz (prochloraz) (B.1.44), fluorine bacterium azoles (triflumizol) (B.1.45)；Miazines, pyridines and piperazines: different phonetic bacterium Alcohol (fenarimol) (B.1.46), nuarimol (nuarimol) (B.1.47), pyrifenox (pyrifenox) (B.1.48), Triforine (triforine) (B.1.49), [3- (the chloro- 2- fluorophenyl of 4-) -5- (2,4 difluorobenzene base) is differentAzoles -4- base] - (3- pyridyl group) methanol (B.1.50)；

Δ 14- reductase inhibitor: 4- dodecyl -2,6- thebaine (aldimorph) (B.2.1), dodemorfe (dodemorph) (B.2.2), dodemorfe acetic acid esters (dodemorph-acetate) (B.2.3), butadiene morpholine (fenpropimorph) (B.2.4), tridemorph (tridemorph) (B.2.5), fenpropidin (fenpropidin) (B.2.6), Pipron (piperalin) (B.2.7), spiral shellLuxuriant amine (spiroxamine) (B.2.8)；

ChlC4 inhibitor: fenhexamid (fenhexamid) (B.3.1)；

C) nucleic acid synthetic inhibitor

Phenylamide or acyl amino acids fungicide: M 9834 (benalaxyl) (C.1.1), smart M 9834 (benalaxyl-M) (C.1.2), kiralaxyl (C.1.3), metalaxyl (metalaxyl) (C.1.4), Metalaxyl-M (metalaxyl-M) (mefenoxam, C.1.5), fenfuram (ofurace) (C.1.6),White spirit (oxadixyl) (C.1.7)；

Other: hydroxyisoxazole (hymexazole) (C.2.1), different thiophene bacterium ketone (octhilinone) (C.2.2), oxolinic acid The phonetic bacterium of (oxolinic acid) (C.2.3), sulphur clever (bupirimate) (C.2.4), 5-flurocytosine (C.2.5), the fluoro- 2- of 5- (p-methylphenyl methoxyl group) pyrimidine -4- amine (C.2.6), the fluoro- 2- of 5- (4- fluorophenylmethoxy) pyrimidine -4- amine (C.2.7)；

D) cell division and cytoskeleton inhibitor

Antitubulin, such as benzimidazole, thiophanate class (thiophanate): benomyl (benomyl) (D1.1), carbendazim (carbendazim) (D1.2), furidazol (fuberidazole) (D1.3), Apl-Luster (thiabendazole) (D1.4), thiophanate methyl (thiophanate-methyl) (D1.5)；Triazolo pyrimidine class: 5- is chloro- 7- (4- methyl piperidine -1- base) -6- (2,4,6- trifluorophenyl)-[1,2,4] triazol [1,5-a] pyrimidine (D1.6)；

Other cell division inhibitors: diethofencarb (diethofencarb) (D2.1), Guardian (ethaboxam) (D2.2), Pencycuron (pencycuron) (D2.3), fluopicolide (fluopicolide) (D2.4), zoxamide (zoxamide) (D2.5), metrafenone (metrafenone) (D2.6), pyriofenone (D2.7)；

E) amino acid and protein synthetic inhibitor

Methionine synthetic inhibitor (anilino-pyrimidine): cyclopropyl pyrimidine (cyprodinil) (E.1.1), mepanipyrim (mepanipyrim) (E.1.2), pyrimethanil (pyrimethanil) (E.1.3)；

Protein synthesis inhibitor: blasticidin-S (blasticidin-S) (E.2.1), spring thunder are plain (kasugamycin) (E.2.2), hydration spring thunder plain (kasugamycinhydrochloride-hydrate) (E.2.3), midolthromycin (mildiomycin) (E.2.4), streptomysin (streptomycin) (E.2.5), terramycin (oxytetracyclin) (E.2.6), Polyoxin (polyoxine) (E.2.7), jinggangmeisu (validamycin A) (E.2.8)；

F) signal transduction inhibitor

- MAP/ Protein histidine kinase inhibitor: fluorine bacterium peace (fluoroimid) (F.1.1), isopropyl are fixed (iprodione) (F.1.2), sharp (procymidone) (F.1.3), vinclozolin (vinclozolin) (F.1.4), fenpiclonil are sterilized (fenpiclonil) (F.1.5), fluorineBacterium (fludioxonil) (F.1.6)；

G-protein inhibitor: quinoxyfen (quinoxyfen) (F.2.1)；

G) lipoid and film synthetic inhibitor

Phosphatide biosynthesis inhibitor: Hinosan (edifenphos) (G.1.1), different rice blast net (iprobenfos) (G.1.2), Ppyrazophos (pyrazophos) (G.1.3), Isoprothiolane (isoprothiolane) (G.1.4)；

It is lipid peroxidized: botran (dicloran) (G.2.1), pentachloronitrobenzene (quintozene) (G.2.2), four Chloronitrobenzene (tecnazene) (G.2.3), tolelofos-methyl (tolclofos-methyl) (G.2.4), biphenyl (G.2.5), Cyclopentadienyl scattered (chloroneb) (G.2.6), kobam (etridiazole) (G.2.7)；

Phosphatide biosynthesis and cell wall deposition: dimethomorph (dimethomorph) (G.3.1), flumorph (flumorph) (G.3.2), mandipropamid (mandipropamid) (G.3.3), pyrimorph (pyrimorph) (G.3.4), benzene metsulfovax (benthiavalicarb) (G.3.5), iprovalicarb (iprovalicarb) (G.3.6), Valifenalate (G.3.7) and N- (1- (1- (4- cyano-phenyl) ethylsulfonyl) butyl- 2- yl) carbamic acid 4- fluorobenzene base ester (G.3.8)；

Influence the compound and fatty acid of cell membrane permeability: hundred tie up clever (propamocarb) (G.4.1)；

Inhibitors of fatty acid amide hydrolase: oxathiapiprolin (G.5.1), methanesulfonic acid 2- 3- [2- (1- [3, 5- bis- (difluoromethyl -1H- pyrazol-1-yl] acetyl group } piperidin-4-yl) -1,3- thiazole-4-yl] -4,5- dihydro -1,2- Azoles -5- base } phenylester (G.5.2), methanesulfonic acid 2- { 3- [2- (1- { [(the difluoromethyl) -1H- of 3,5- bis- pyrazol-1-yl] acetyl Base } piperidin-4-yl) -1,3- thiazole-4-yl] -4,5- dihydro -1,2-Azoles -5- base } -3- chlorobenzene base ester (G.5.3)；

H) with the inhibitor of multidigit point effect

Inorganic active materia: Bordeaux mixture (Bordeaux mixture) (H.1.1), copper acetate (H.1.2), Kocide SD (H.1.3), Cupravit (copper oxychloride) (H.1.4), basic copper sulfate (H.1.5), sulphur (H.1.6)；

Thio-and dithiocarbamate: fervam (ferbam) (H.2.1), Mancozeb (mancozeb) (H.2.2), maneb (maneb) (H.2.3), metham-sodium (metam) (H.2.4), Carbatene (metiram) (H.2.5), methyl Zineb (propineb) (H.2.6), thiram (thiram) (H.2.7), zineb (zineb) (H.2.8), ziram (ziram)(H.2.9)；

Organochlorine compound (such as phthalimide class, sulfonyl amine, chloro nitrile): anilazine (anilazine) (H.3.1), Bravo (chlorothalonil) (H.3.2), difoltan (captafol) (H.3.3), gram bacterium Red (captan) (H.3.4), folpet (folpet) (H.3.5), Euparen (dichlofluanid) (H.3.6), antiphen (dichlorophen) (H.3.7), hexachloro-benzene (H.3.8), pentachlorophenol (pentachlorphenole) (H.3.9) and its salt, four Chlorobenzene phthalein (phthalide) (H.3.10), tolyfluanid (tolylfluanid) (H.3.11), N- (the chloro- 2- nitrobenzene of 4- Base)-N- ethyl -4- methyl benzenesulfonamide (H.3.12)；

Guanidine and other: guanidine (H.4.1), dodine (H.4.2), dodine free alkali (H.4.3), Guanoctine (guazatine) (H.4.4), iminoctadine (guazatine-acetate) (H.4.5), biguanide spicy acid salt (iminoctadine) (H.4.6), iminoctadine triacetate (iminoctadine-triacetate) (H.4.7), double eight guanidines Salt (iminoctadine-tris (albesilate)) (H.4.8), Delan's (dithianon) (H.4.9), 2,6- dimethyl- 1H, 5H- [1,4] dithiadiene simultaneously [2,3-c:5,6-c'] joins pyrroles -1,3,5,7 (2H, 6H)-tetrone (H.4.10)；

I) Cell wall synthesis inhibitor

Glucan synthetic inhibitor: jinggangmeisu (validamycin) (I.1.1), Polyoxin (polyoxinB) (I.1.2)；

Melanin genesis inhibitor: pyroquilon (pyroquilon) (I.2.1), tricyclazole (tricyclazole) (I.2.2), carpropamide (carpropamid) (I.2.3), double chlorine zarilamid (dicyclomet) (I.2.4), zarilamid (fenoxanil)(I.2.5)；

J) plant defense inducing agent

It is thiadiazoles element (acibenzolar-S-methyl) (J.1.1), probenazole (probenazole) (J.1.2), different Metsulfovax (isotianil) (J.1.3), tiadinil (tiadinil) (J.1.4), Prohexadione calcium (prohexadione- calcium)(J.1.5)；Phosphonic acid ester: fosetyl (fosetyl) (J.1.6), aliette (fosetyl-aluminum) (J.1.7), phosphorous acid and its salt (J.1.8), saleratus or sodium (J.1.9)；

K) unknown role mode

Bronopol (bronopol) (K.1.1), go out mite grasshopper (chinomethionat) (K.1.2), cyflufenamid (cyflufenamid) (K.1.3), cymoxanil (cymoxanil) (K.1.4), dazomet (dazomet) (K.1.5), debacarb (debacarb) (K.1.6), diclomezine (diclomezine) (K.1.7), difenzoquat (difenzoquat) (K.1.8), wild swallow Withered methylsulfuric acid ester (difenzoquat-methylsulfate) (K.1.9), diphenylamines (K.1.10), amine benzene pyrrole bacterium ketone (fenpyrazamine) (K.1.11), fluorine biphenyl bacterium (flumetover) (K.1.12), flusulfamide (flusulfamide) (K.1.13), flutianil (K.1.14), methasulfocarb (methasulfocarb) (K.1.15), N-Serve (nitrapyrin) (K.1.16), isopropyl disappear (nitrothal-isopropyl) (K.1.18), oxathiapiprolin (K.1.19), Tolprocarb (K.1.20), copper 8-hydroxyquinolinate (oxin-copper) (K.1.21), the third oxygen quinoline (proquinazid) (K.1.22), Tebufloquin (K.1.23), tecloftalam (K.1.24), azoles bacterium piperazine (triazoxide) (K.1.25), 2- butoxy -6- are iodo- 3- propyl benzopyran-4-one ketone (K.1.26), 2- [(the difluoromethyl) -1H- of 3,5- bis- pyrazol-1-yl] -1- [4- (4- { 5- [2- (propyl- 2- alkynes -1- base oxygroup) phenyl] -4,5- dihydro -1,2-Azoles -3- base } -1,3- thiazol-2-yl) piperidin-1-yl] ethyl ketone (K.1.27), 2- [(the difluoromethyl) -1H- of 3,5- bis- pyrazol-1-yl] -1- [4- (4- { 5- [the fluoro- 6- of 2- (propyl- 2- alkynes -1- base oxygen Base) phenyl] -4,5- dihydro -1,2-Azoles -3- base } -1,3- thiazol-2-yl) piperidin-1-yl] ethyl ketone (K.1.28), 2- [3, (the difluoromethyl) -1H- of 5- bis- pyrazol-1-yl] -1- [4- (4- { 5- [the chloro- 6- of 2- (propyl- 2- alkynes -1- base oxygroup) phenyl] -4,5- Dihydro -1,2-Azoles -3- base } -1,3- thiazol-2-yl) piperidin-1-yl] ethyl ketone (K.1.29), N- (cyclopropyl-methoxy imido Base-(6- difluoro-methoxy -2,3- difluorophenyl) methyl) -2- phenyl-acetamides (K.1.30), N'- (4- (the chloro- 3- fluoroform of 4- Phenoxyl) -2,5- 3,5-dimethylphenyl)-N- ethyl-N-methyl carbonamidine (K.1.31), N'- (4- (the fluoro- 3- trifluoromethylbenzene of 4- Oxygroup) -2,5- 3,5-dimethylphenyl)-N- ethyl-N-methyl carbonamidine (K.1.32), N'- (2- methyl -5- trifluoromethyl -4- (3- tri- Methyl-monosilane base propoxyl group) phenyl)-N- ethyl-N-methyl carbonamidine (K.1.33), N'- (5- difluoromethyl -2- methyl -4- (3- Trimethylsilyl propoxyl group) phenyl)-N- ethyl-N-methyl carbonamidine (K.1.34), methoxyacetic acid 6- tert-butyl -8- fluoro- 2, [5- (4- aminomethyl phenyl) -2,3- dimethyl is different by 3- dimethyl quinoline -4- base ester (K.1.35), 3-Oxazolidine -3- base] pyridine (K.1.36), [5- (4- chlorphenyl) -2,3- dimethyl is different by 3-Oxazolidine -3- base] pyridine (pyrisoxazole) (K.1.37), N- (6- methoxypyridine -3- base) cyclopropane carboxamide (K.1.38), the chloro- 1- of 5- (4,6- dimethoxypyridin -2- base) -2- first Base -1H- benzimidazole (K.1.39), [4- (3,4- Dimethoxyphenyl) is different by 2- (4- chlorine chlorphenyl)-N-Azoles -5- base] -2- Propyl- 2- alkynyloxy group acetamide, (Z) -3- amino -2- cyano -3- Cinnamic Acid ethyl ester (K.1.40), picarbutrazox (K.1.41), N- [6- [[(Z)-[(1- methyl tetrazolium -5- base) phenylmethylene] amino] oxygroup methyl] -2- pyridyl group] amino Amyl formate (K.1.42), 2- [2- [(bis- fluoro-2-methyl-3-quinolin base of 7,8-) oxygroup] -6- fluoro-phenyl] propan-2-ol (K.1.43), 2- [the fluoro- 6- of 2- [(8- fluoro-2-methyl-3-quinolin base) oxygroup] phenyl] propan-2-ol (K.1.44), (5- is fluoro- by 3- 3,3,4,4- tetramethyl -3,4- dihydro-isoquinoline -1- base) quinoline (K.1.45), 3- (the fluoro- 3,3- dimethyl -3,4- two of 4,4- bis- Hydrogen isoquinoline -1- base) quinoline (K.1.46), 3- (the fluoro- 3,3- dimethyl -3,4- dihydro-isoquinoline -1- base of 4,4,5- tri-) quinoline (K.1.47), the fluoro- 2,2- dimethyl -5- of 9- (3- quinolyl) -3H-1,4- benzo oxygen azepine(K.1.48)；

L)

M) insecticide

M.1) be selected from acetylcholinesterase (AChE) inhibitor of following classification: M.1A carbamates, such as tears go out Prestige (aldicarb), alanycarb (alanycarb),Worm prestige (bendiocarb), Benfuracard micro (benfuracarb), fourth Ketone prestige (butocarboxim), butanone oxygen prestige (butoxycarboxim), carbaryl (carbaryl), furadan (carbofuran), carbosulfan (carbosulfan), benzene worm prestige (ethiofencarb), Bassa (fenobucarb), Anti- mite amidine (formetanate), furathiocarb (furathiocarb), Mobucin (isoprocarb), mercaptodimethur (methiocarb), methomyl (methomyl), MTMC (metolcarb), methomyl (oxamyl), Aphox (pirimicarb), arprocarb (propoxur), thiodicarb (thiodicarb), thiofanox (thiofanox), Landrin (trimethacarb), XMC, Meobal (xylylcarb) and triaguron (triazamate)；Or M.1B organophosphorus ester Class, such as accephate (acephate), azoles pyridine phosphorus (azamethiphos), triazotion (azinphos-ethyl), paddy sulphur Phosphorus (azinphosmethyl), cadusafos (cadusafos), chlorethoxyfos (chlorethoxyfos), chlorfenviphos (chlorfenvinphos), chlormephos (chlormephos), chlopyrifos (chlorpyrifos), chlorpyrifos-methyl (chlorpyrifos-methyl), Resistox (coumaphos), cynock (cyanophos), demeton-methyl (demeton- S-methyl), basudin (diazinon), DDVP (dichlorvos/DDVP), Carbicron (dicrotophos), Rogor (dimethoate), dimethylvinphos (dimethylvinphos), disulfoton (disulfoton), EPN, Ethodan (ethion), ethoprop (ethoprophos), famphur (famphur), fenamiphos (fenamiphos), Folithion (fenitrothion), Entex (fenthion), colophonate (fosthiazate), heptenophos (heptenophos), new Nicotinoids (imicyafos), isofenphos (isofenphos), O- (Methoxyamino thiophosphoryl) isopropyl salicylate, It is differentAzoles phosphorus (isoxathion), malathion (malathion), Afos (mecarbam), acephatemet (methamidophos), methidathion (methidathion), Menite (mevinphos), Azodrin (monocrotophos), 2-dichloroethylk dimethyl phosphate (naled), omethoate (omethoate), metilomerkaptofosoksid (oxydemeton-methyl), 1 (parathion), parathion-methyl (parathion-methyl), phenthoate dimephenthoate cidial (phenthoate), thimet (phorate), Zolone (phosalone), phosmet (phosmet), phosphamidon (phosphamidon), phoxim (phoxim), Actellic (pirimiphos-methyl), Profenofos (profenofos), Propetamphos (propetamphos), Toyodan (prothiofos), pyraclofos (pyraclofos), pyridaphethione (pyridaphenthion), quinalphos (quinalphos), sulfotep (sulfotep), butyl pyrimidine phosphorus (tebupirimfos), Swebate (temephos), special fourth Phosphorus (terbufos), tetrachlorvinphos (tetrachlorvinphos), thiometon (thiometon), Hostathion (triazophos), metrifonate (trichlorfon) and vamidothion (vamidothion)；

M.2) GABA gated chloride channel antagonist, such as M.2A cyclic diolefine organochlorine compound, such as 5a,6,9,9a-hexahydro-6,9-methano-2,4 (endosulfan) or Niran (chlordane)；Or M.2B fiproles (phenyl pyrazoles), such as ethiprole (ethiprole), Frontline (fipronil), butene-fipronil (flufiprole), pyrafluprole and pyriprole；

M.3 the sodium channel modulators of following classification: M.3A pyrethroids, such as acrinathrin) are selected from (acrinathrin), Pynamin (allethrin), d-allethrin (D-cis-transallethrin), dextrorotation are anti- Formula allethrin (D-trans allethrin), bifenthrin (bifenthrin), bioallethrin (bioallethrin), 2- cyclopentenyl bioallethrin (bioallethrin S-cyclopentenyl), biological benzyl furan Pyrethroids (bioresmethrin), cycloprothrin (cycloprothrin), cyfloxylate (cyfluthrin), efficient cyfluthrin Pyrethroids (beta-cyfluthrin), (RS) lambda-cyhalothrin (cyhalothrin), lambda-cyhalothrin (lambda- Cyhalothrin), smart gamma cyhalothrin (gamma-cyhalothrin), cypermethrin (cypermethrin), nail body Cypermethrin (alpha-cypermethrin), Cypermethrin (beta-cypermethrin), beta-cypermethrin (theta-cypermethrin), own body cypermethrin (zeta-cypermethrin), cyphenothrin (cyphenothrin), decis (deltamethrin), Prallethrin (empenthrin), esfenvalerate (esfenvalerate), ethofenprox (etofenprox), Fenpropathrin (fenpropathrin), killing pyrethroids (fenvalerate), flucythrinate (flucythrinate), flumethrin (flumethrin), taufluvalinate (tau-fluvalinate), bromine fluorine ethofenprox (halfenprox), heptafluthrin, miaow alkynes pyrethroids (imiprothrin), Fluorine chlorine ether pyrethroids (meperfluthrin), metofluthrin (metofluthrin), momfluorothrin, Permethrin (permethrin), phenothrin (phenothrin), prallethrin (prallethrin), the third Flumethrin (profluthrin), pyrethrins (pyrethrin (Dalmatian chrysanthemum (pyrethrum))), Chryson (resmethrin), deinsectization Silicon ether (silafluofen), Tefluthrin (tefluthrin), etrafluorine ethofenprox (tetramethylfluthrin), tetramethrin (tetramethrin), tralomethrin (tralomethrin) and transfluthrin (transfluthrin)；Or M.3B sodium channel tune Save agent such as DDT or methoxychlor (methoxychlor)；

M.4) it is selected from the nicotinic acetylcholine receptor agonist (nAChR) of following classification: M.4A anabasine, such as pyrrole Worm clear (acetamiprid), clothianidin (chlothianidin), cycloxaprid (cycloxaprid), dinotefuran (dinotefuran), imidacloprid (imidacloprid), nitenpyram (nitenpyram), thiacloprid (thiacloprid) and Diacloden (thiamethoxam)；Or compound is M.4A.2:(2E-) -1- [(6- chloropyridine -3- base) methyl]-N'- nitro - 2- pentylidene aminoguanidine；Or M4.A.3:1- [(6- chloropyridine-3- base) methyl] propoxyl group-1,2-7- methyl-8- nitro-5-, 3,5,6,7- hexahydro imidazo [1,2-a] pyridine；Or M.4B nicotine (nicotine)；

M.5 the nAChR allosteric activator of pleocidin classification, such as spinosad) are selected from (spinosad) or ethyl pleocidin (spinetoram)；

M.6 avermectin and the other chloride channel activator of milbemycins, such as Olivomitecidin) are selected from (abamectin), emamectin-benzoate (emamectin benzoate), ivermectin (ivermectin), Lepimectin or milbemycin (milbemectin)；

M.7) juvenile hormone mimics, such as M.7A juvenoid, such as cover 512 (hydroprene), kinoprene (kinoprene) and Entocon ZR 515 (methoprene)；Or other such as M.7B shuangweiwei (fenoxycarb) or M.7C pyriproxyfen (pyriproxyfen)；

M.8) other non-specific (multidigit point) inhibitor, such as M.8A alkyl halide such as bromomethane and other alkyl halides Compound, or M.8B chloropicrin (chloropicrin), or M.8C sulfuryl fluoride (sulfurylfluoride), or M.8D borax, or M.8E potassium antimonyl tartrate (tartar emetic)；

M.9) selective Homoptera insect feeds blocking agent, such as M.9B pymetrozine (pymetrozine) or M.9C fluorine pyridine Insect amide (flonicamid)；

M.10) acarid growth inhibitor, such as M.10A clofentezine (clofentezine), Hexythiazox (hexythiazox) With flufenzine (diflovidazin), or M.10B special benzeneAzoles (etoxazole)；

M.11) the microorganism agent interfering of insect midgut film, such as bacillus thuringiensis (bacillus Thuringiensis) or Bacillus sphaericus (bacillus sphaericus) and they generate insecticidal proteins such as Su Yun Golden bacillus Israel subclass (bacillus thuringiensis subsp.israelensis), Bacillus sphaericus, Thuringiensis Aizawa subspecies (bacillus thuringiensis subsp.aizawai), bacillus Thuringiensis subsp.kurstaki and Bacillus thuringiensis subsp. tenebrionis bacterial strain (bacillus Thuringiensis subsp.tenebrionis) or Bt crop albumen: Cry1Ab, Cry1Ac, Cry1Fa, Cry2Ab, MCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1；

M.12) mitochondrial ATP synthesis inhibitor, such as M.12A mite killing sulphur is grand (diafenthiuron) or M.12B organic Tin acaricide, such as azacyclotin (azocyclotin), plictran (cyhexatin) or fenbutatin oxide (fenbutatin oxide), or M.12C propargite (propargite), or M.12D tetradiphon (tetradifon)；

M.13 it) uncouples agent, such as chlorfenapyr (chlorfenapyr), two via the oxidative phosphorylation that proton gradient is interfered Nitre phenol (DNOC) or sulfluramid (sulfluramid)；

M.14) nAChR (nAChR) channel blocker, such as nereistoxin is similar to object, such as bensultap (bensultap), cartap (cartap hydrochloride), thiocyclam (thiocyclam) or dimehypo (thiosultap sodium)；

M.15) 0 benzoylurea derivertives of type such as benzoyl area kind, such as bistrifluron (bistrifluron), UC 62644 (chlorfluazuron), fluorourea (diflubenzuron), flucycloxuron (flucycloxuron), flufenoxuron (flufenoxuron), flubenzuron (hexaflumuron), fluorine the third oxygen urea (lufenuron), Rimon (novaluron), polyfluoro worm uride (noviflumuron), Teflubenzuron (teflubenzuron) or insecticidal lung (triflumuron)；

M.16) Class1 benzoylurea derivertives such as Buprofezin (buprofezin)；

M.17) dipteral insect husking agent interfering, such as cyromazine (cyromazine)；

M.18) ecdysone receptor stimulating agent such as two hydrazides, such as Runner (methoxyfenozide), double benzene Hydrazides (tebufenozide), Benzoic acid N-tert-butyl-N-(4-chlorobenzoyl)hydrazide (halofenozide), furan tebufenozide (fufenozide) or ring tebufenozide (chromafenozide)；

M.19) octopamine receptor agonist (Octopamin receptor agonsit), such as Amitraz (amitraz)；

M.20) mitochondria complex III electron-transport inhibitor, such as M.20A amdro (hydramethylnon), or M.20B acequinocyl (acequinocyl), or M.20C fluacrypyrim (fluacrypyrim)；

M.21) mitochondria complex I electron-transport inhibitor, such as M.21A METI acaricide and insecticide, such as quinoline mite Ether (fenazaquin), fenpyroximate (fenpyroximate), pyrimidifen (pyrimidifen), pyridaben (pyridaben), pyrrole Mite amine (tebufenpyrad) or Tolfenpyrad (tolfenpyrad), or M.21B rotenone (rotenone)；

M.22) voltage gated sodium channel blocking agent, such as M.22ADiazole worm (indoxacarb), or M.22B cyanogen Sulfluramid (metaflumizone), or M.22B.1:2- [2- (4- cyano-phenyl) -1- [3- trifluoromethyl] ethylidene] ammonia Base]-N- [4- (difluoro-methoxy) phenyl] semicarbazides or M.22B.2:N- (3- chloro-2-methyl phenyl) -2- [(4- chlorphenyl) [4- [methyl (methyl sulphonyl) amino] phenyl] methylene] semicarbazides；

M.23) acetyl CoA carboxylase inhibitor, such as sour (Tetramic acid) derivative of tetronic acid and tetramino, such as Envidor (spirodiclofen), Spiromesifen (spiromesifen) or spiral shell worm ethyl ester (spirotetramat)；

M.24) mitochondria complex IV electron-transport inhibitor, such as M.24A phosphine such as aluminum phosphate, calcium phosphide, phosphine or phosphorus Change zinc, or M.24B cyanide；

M.25) mitochondria complex II electron-transport inhibitor, such as ss-ketonitriles derivative, such as nitrile pyrrole mite ester (cyenopyrafen) or cyflumetofen (cyflumetofen)；

M.28 the other Ryanicide of diamide (Ryanodine) receptor modulators, such as Flubendiamide) are selected from (flubendiamide), chlorantraniliprole (chlorantraniliprole)Cyanogen insect amide (cyantraniliprole)Fluorine cyanogen insect amide (tetraniliprole) or phthalyl amine compounds Object is M.28.1:(R) the chloro- N1- of -3- { 2- methyl -4- [1,2,2,2- tetra- fluoro- 1- (trifluoromethyl) ethyl] phenyl }-N2- (1- first Base -2- methysulfonylethyl) phthalic amide and M.28.2:(S) { [1,2,2,2- tetra- is fluoro- by 2- methyl -4- by the chloro- N1- of -3- 1- (trifluoromethyl) ethyl] phenyl }-N2- (1- methyl -2- methysulfonylethyl) phthalic amide or compound M.28.3:3- bromo- N- { the chloro- 6- of the bromo- 4- of 2- [(1- cyclopropylethyl) carbamoyl] phenyl } -1- (3- chloropyridine -2- base) - 1H- pyrazoles -5- formamide (it is recommended that ISO name: cyclaniliprole) or compound M.28.4:2- [3,5- bis- bromo- 2- ({ [the bromo- 1- of 3- (3- chloropyridine -2- base) -1H- pyrazoles -5- base] carbonyl } amino) benzoyl] -1,2- dimethylhydrazine formic acid first Ester；Or selected from M.28.5a)-M.28.5d) and M.28.5h)-M.28.5l) compound: M.28.5a) N- [the chloro- 2- of 4,6- bis- [(diethyl-λ -4- sulfurous alkyl (sulfanylidene)) carbamoyl] phenyl] -2- (3- chloro-2-pyridyl) -5- three Methyl fluoride pyrazole-3-formamide；M.28.5b) N- [the chloro- 2- of 4- [(diethyl-λ -4- sulfurous alkyl) carbamoyl] -6- first Base phenyl] -2- (3- chloro-2-pyridyl) -5- trifluoromethyl pyrazol -3- formamide；M.28.5c) N- [the chloro- 2- of 4- [(two -2- third Base-λ -4- sulfurous alkyl) carbamoyl] -6- aminomethyl phenyl] -2- (3- chloro-2-pyridyl) -5- trifluoromethyl pyrazol -3- first Amide；M.28.5d) (3- is chloro- by -2- by N- [the chloro- 2- of 4,6- bis- [(two -2- propyl-λ -4- sulfurous alkyl) carbamoyl] phenyl] 2- pyridyl group) -5- trifluoromethyl pyrazol -3- formamide；M.28.5h) N- [the bromo- 2- of 4,6- bis- [(diethyl-λ -4- sulfurous alkane Base) carbamoyl]-phenyl] -2- (3- chloro-2-pyridyl) -5- trifluoromethyl pyrazol -3- formamide；M.28.5i)N-[2- (5- amino -1,3,4- thiadiazoles -2- base) chloro- 6- aminomethyl phenyl of -4-] the bromo- 2- of -5- (3- chloro-2-pyridyl) -1H- pyrazoles -5- Formamide；M.28.5j) the chloro- 1- of 3- (3- chloro-2-pyridyl)-N- [the chloro- 6- of 2,4- bis- [[(1- cyano -1- Methylethyl) ammonia Base] carbonyl] phenyl] -1H- pyrazoles -5- formamide；M.28.5k) the bromo- N- of 3- [2,4- bis- chloro- 6- (methylcarbamoyl) benzene Base] -1- (3,5- dichloro-2-pyridyl base) -1H- pyrazoles -5- formamide；M.28.5l) N- [the chloro- 2- of 4- [[(1,1- dimethyl second Base) amino] carbonyl] -6- aminomethyl phenyl] -1- (3- chloro-2-pyridyl) -3- fluorine methoxyl group -1H- pyrazoles -5- formamide；Or choosing From following compound: M.28.6:N- two formyl of (2- cyano propyl- 2- yl)-N- (2,4- 3,5-dimethylphenyl) -3- iodobenzene -1,2- Imines；Or M.28.7:3- chloro- N- (2- cyano propyl- 2- yl)-N- (2,4- 3,5-dimethylphenyl) benzene -1,2- dicarboximide；

M.29) unknown or uncertain binding mode insecticidal active compound, such as afidopyropen, Afoxolaner, nimbin (azadirachtin), sulfanilamide (SN) mite ester (amidoflumet), Citrazon (benzoximate), connection Phenylhydrazine ester (bifenazate), broflanilide, fenisobromolate (bromopropylate), oxolinic acide (chinomethionat), ice crystal (cryolite), dicloromezotiaz, dicofol (dicofol), phonetic worm amine (flufenerim), flometoquin, fluorine thiophene worm sulfone (fluensulfone), fluhexafon, fluopyram (fluopyram)、flupyradifurone、fluralaner、Worm ketone (metoxadiazone), Butacide (piperonyl butoxide), pyflubumide, pyridalyl (pyridalyl), pyrifluquinazon, flonicamid Nitrile (sulfoxaflor), tioxazafen, triflumezopyrim or compound

M.29.3:11- two spiral shell of (the chloro- 2,6- 3,5-dimethylphenyl of 4-) -12- hydroxyl -1,4- dioxa -9- azepine [4.2.4.2] 14 carbon -11- alkene -10- ketone or compound M.29.4:3- (fluoro- 2, the 4- dimethyl diphenyl -3- base of 4'-) -4- hydroxyl Base -8- oxa- -1- azaspiro [4.5] decyl- 3- alkene -2- ketone or compound M.29.5:1- [the fluoro- 4- methyl -5- [(2,2,2- of 2- Trifluoroethyl) sulfinyl] phenyl] and -3- Trifluoromethyl-1 H-1,2,4- triazole -5- amine or be based on bacillus firmus The active matter (Votivo, I-1582) of (bacillus firmus)；Or selected from the compound M.29.6 organized, the wherein compound Selected from M.29.6a) to M.29.6k): M.29.6a) (E/Z)-N- [1- [(6- chloro-3-pyridyl base) methyl] -2- sub-pyridyl group] - 2,2,2- trifluoroacetamide；M.29.6b) (E/Z)-N- [1- [(the chloro- 5- fluoro-3-pyridine base of 6-) methyl] -2- sub-pyridyl group] -2, 2,2- trifluoroacetamide；M.29.6c) the fluoro- N- of (E/Z) -2,2,2- three [1- [(the 6- fluoro-3-pyridine base) methyl] Asia -2- pyridine Base] acetamide；M.29.6d) (E/Z)-N- [1- [(the bromo- 3- pyridyl group of 6-) methyl] -2- sub-pyridyl group] -2,2,2- trifluoroacetyl Amine；M.29.6e) (E/Z)-N- [1- [1- (6- chloro-3-pyridyl base) ethyl] -2- sub-pyridyl group] -2,2,2- trifluoroacetamide； M.29.6f) two Fluorakil 100 of (E/Z)-N- [1- [(6- chloro-3-pyridyl base) methyl] -2- sub-pyridyl group] -2,2-；M.29.6g) (E/Z) two Fluorakil 100 of the chloro- N- of -2- [1- [(6- chloro-3-pyridyl base) methyl] -2- sub-pyridyl group] -2,2-；M.29.6h)(E/ Z)-N- [1- [(2- chlorine pyrimidine -5- base) methyl] -2- sub-pyridyl group] -2,2,2- trifluoroacetamide；M.29.6i)(E/Z)-N- Five fluoroalanine of [1- [(6- chloro-3-pyridyl base) methyl] -2- sub-pyridyl group] -2,2,3,3,3-；M.29.6j)N-[1-[(6- Chloro-3-pyridyl base) methyl] -2- sub-pyridyl group] -2,2,2- trifluoro thioacetamide；Or M.29.6k) N- [1- [(the chloro- 3- pyrrole of 6- Piperidinyl) methyl] -2- sub-pyridyl group] three fluoro- N'- isopropyl yl acetamide of -2,2,2-；Or compound M.29.8:8- chloro- N- [2- Chloro-5-methoxyl phenyl) sulfonyl] -6- trifluoromethyl) imidazo [1,2-a] pyridine-2-carboxamide；Or compound M.29.9a): [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4H- is different by 4-Azoles -3- base] -2- methyl-N- (1- oxo thia Ding Huan -3- base) benzamide；Or M.29.9.b): [5- (3,5- dichlorophenyl) -5- trifluoromethyl -4,5- dihydro is different by 4- Azoles -3- base]-N- [(methoxyimino) methyl] -2- methyl benzamide；Or M.29.10:5- [3- [chloro- 4- (the 3,3- of 2,6- bis- Two chloroallyloxyaminos) phenoxy group] propoxyl group] -1H- pyrazoles；Or selected from the compound M.29.11 organized, wherein the compound is selected from M.29.11b) to M.29.11p): M.29.11.b) 3- (benzoylmethyl amino)-N- [the bromo- 4- of 2- [1,2,2,3,3,3- six Fluoro- 1- trifluoromethylpropyl] -6- trifluoromethyl] -2- fluorobenzamide；M.29.11.c) 3- (benzoylmethyl ammonia Base) the fluoro- N- of -2- [the iodo- 4- of 2- [the fluoro- 1- trifluoromethyl ethyl of 1,2,2,2- tetra-] -6- trifluoromethyl] benzamide； M.29.11.d) N- [3- [[[the iodo- 4- of 2- [the fluoro- 1- trifluoromethyl ethyl of 1,2,2,2- tetra-] -6- trifluoromethyl] amino] carbonyl Base] phenyl]-N-methyl-benzamide；M.29.11.e) N- [3- [[[the bromo- 4- of 2- [the fluoro- 1- trifluoromethyl second of 1,2,2,2- tetra- Base] -6- trifluoromethyl] amino] carbonyl]] -2- fluorophenyl] the fluoro- N-methyl-benzamide of -4-；M.29.11.f) 4- is fluoro- N- [the fluoro- 3- of 2- [[[the iodo- 4- of 2- [the fluoro- 1- trifluoromethyl ethyl of 1,2,2,2- tetra-] -6- trifluoromethyl] amino] carbonyl] benzene Base]-N-methyl-benzamide；M.29.11.g) the fluoro- N- of 3- [the fluoro- 3- of 2- [[[the iodo- 4- of 2- [the fluoro- 1- fluoroform of 1,2,2,2- tetra- Base ethyl] -6- trifluoromethyl] amino] carbonyl] phenyl]-N-methyl-benzamide；M.29.11.h) chloro- N- [the 3- of 2- [[[the iodo- 4- of 2- [the fluoro- 1- trifluoromethyl ethyl of 1,2,2,2- tetra-] -6- trifluoromethyl] amino] carbonyl] phenyl] -3- pyridine Formamide；M.29.11.i) 4- cyano-N- [2- cyano -5- [[the bromo- 4- of 2,6- bis- [1,2,2,3,3,3- hexafluoro -1- trifluoromethyl Propyl] phenyl] carbamoyl] phenyl] -2- methyl benzamide；M.29.11.j) 4- cyano -3- [(4- cyano -2- methyl Benzoyl) amino]-N- [the chloro- 4- of 2,6- bis- [1,2,2,3,3,3- hexafluoro -1- trifluoromethylpropyl] phenyl] -2- fluorobenzene first Amide；M.29.11.k) N- [5- [[the chloro- 6- cyano -4- of 2- [1,2,2,3,3,3- hexafluoro -1- trifluoromethylpropyl] phenyl] ammonia Base formoxyl] -2- cyano-phenyl] -4- cyano -2- methyl benzamide；M.29.11.l) N- [5- [[the chloro- 4- of the bromo- 6- of 2- [2, The fluoro- 1- hydroxyl -1- trifluoromethyl ethyl of 2,2- tri-] phenyl] carbamoyl] -2- cyano-phenyl] -4- cyano -2- methylbenzene first Amide；M.29.11.m) N- [5- [[the chloro- 4- of the bromo- 6- of 2- [1,2,2,3,3,3- hexafluoro -1- trifluoromethylpropyl] phenyl] amino Formoxyl] -2- cyano-phenyl] -4- cyano -2- methyl benzamide；M.29.11.n) 4- cyano-N- [2- cyano -5- [[2,6- Two chloro- 4- [1,2,2,3,3,3- hexafluoro -1- trifluoromethylpropyl] phenyl] carbamoyl] phenyl] -2- methyl benzamide； M.29.11.o) 4- cyano-N- [2- cyano -5- [[the chloro- 4- of 2,6- bis- [the fluoro- 1- trifluoromethyl ethyl of 1,2,2,2- tetra-] phenyl] Carbamoyl] phenyl] -2- methyl benzamide；M.29.11.p) N- [5- [[the chloro- 4- of the bromo- 6- of 2- [the fluoro- 1- of 1,2,2,2- tetra- Trifluoromethyl ethyl] phenyl] carbamoyl] -2- cyano-phenyl] -4- cyano -2- methyl benzamide；Or selected from M.29.12 The compound of group, wherein M.29.12a the compound is selected from) to M.29.12m): M.29.12.a) (1,3- bis- 2-Alkane -2- Base) -6- [2- (3- pyridyl group) -5- thiazolyl] pyridine；M.29.12.b) 2- [6- [2- (5- fluoro-3-pyridine base) -5- thiazole Base] -2- pyridyl group] pyrimidine；M.29.12.c) 2- [6- [2- (3- pyridyl group) -5- thiazolyl] -2- pyridyl group] pyrimidine； M.29.12.d) N- methyl sulphonyl -6- [2- (3- pyridyl group) thiazole -5- base] pyridine-2-carboxamide；M.29.12.e) N- first Base sulfonyl -6- [2- (3- pyridyl group) thiazole -5- base] pyridine-2-carboxamide；M.29.12.f) N- ethyl-N- [4- methyl -2- (3- pyridyl group) thiazole -5- base] -3- methyl mercapto propionamide；M.29.12.g) N- methyl-N- [4- methyl -2- (3- pyridyl group) thiophene Azoles -5- base] -3- methyl mercapto propionamide；M.29.12.h) N, 2- dimethyl-N-[4- methyl -2- (3- pyridyl group) thiazole -5- Base] -3- methyl mercapto propionamide；M.29.12.i) N- Ethyl-2-Methyl-N- [4- methyl -2- (3- pyridyl group) thiazole -5- base] - 3- methyl mercapto propionamide；M.29.12.j) N- [the chloro- 2- of 4- (3- pyridyl group) thiazole -5- base]-N- Ethyl-2-Methyl -3- first sulphur Base propionamide；M.29.12.k) N- [the chloro- 2- of 4- (3- pyridyl group) thiazole -5- base]-N, 2- dimethyl -3- methyl mercapto propionamide； M.29.12.l) N- [the chloro- 2- of 4- (3- pyridyl group) thiazole -5- base]-N- methyl -3- methyl mercapto propionamide；M.29.12.m)N- [the chloro- 2- of 4- (3- pyridyl group) thiazole -5- base]-N- ethyl -3- methyl mercapto propionamide；Or compound is M.29.14a) [(6- is chloro- by 1- 3- pyridyl group) methyl] -1,2,3,5,6,7- hexahydro -5- methoxyl group -7- methyl -8- nitroimidazole simultaneously [1,2-a] pyridine；Or M.29.14b) 1- [(6- chloropyridine -3- base) methyl] -7- methyl -8- nitro -1,2,3,5,6,7- hexahydro imidazo [1,2-a] Pyridine -5- alcohol；Or compound is M.29.16a) 1- isopropyl-N, 5- dimethyl-N-pyridazine -4- base pyrazole-4-carboxamide；Or M.29.16b) 1- (1,2- dimethyl propyl)-N- ethyl -5- methyl-N- pyridazine -4- base pyrazole-4-carboxamide；M.29.16c) N, 5- dimethyl-N-pyridazine -4- base -1- (the fluoro- 1- Methylethyl of 2,2,2- tri-) pyrazole-4-carboxamide；M.29.16d)1-[1- (1- anocy clopropyl) ethyl]-N- ethyl -5- methyl-N- pyridazine -4- base pyrazole-4-carboxamide；M.29.16e) N- ethyl -1- (the fluoro- 1- methyl-propyl of 2-) -5- methyl-N- pyridazine -4- base pyrazole-4-carboxamide；M.29.16f) 1- (1,2- dimethyl propylene Base)-N, 5- dimethyl-N-pyridazine -4- base pyrazole-4-carboxamide；M.29.16g) 1- [1- (1- anocy clopropyl) ethyl]-N, 5- dimethyl-N-pyridazine -4- base pyrazole-4-carboxamide；M.29.16h) N- methyl-1-(the fluoro- 1- methyl-propyl of 2-]-5- methyl- N- pyridazine -4- base pyrazole-4-carboxamide；M.29.16i) 1- (4,4- difiuorocyclohexyl)-N- ethyl -5- methyl-N- pyridazine -4- Base pyrazole-4-carboxamide；Or M.29.16j) 1- (4,4- difiuorocyclohexyl)-N, 5- dimethyl-N-pyridazine -4- base pyrazoles -4- first Amide；

N) herbicide

It is selected from the herbicide of following classification: ethanamide, amides, aryloxyphenoxypropionate class, benzamide Class, benzofuran, benzoic acids, benzothiadiazine ketone, bipyridyl, carbamates, chloro-acetyl amine, chloro It is carboxylic acid, cyclohexane diketone, dinitroaniline, dinitrophenol, diphenyl ether, glycine class, imidazolone type, different It is azole, different(oxazolidinon-5-yl-methyl)-2-thiophene-carboxamides, nitrile, N- phenyl phthalimide class,Diazoles,Oxazolidinedione class, hydroxyl acetyl Amine, phenoxy carboxylic acid class, carbanilate class, phenyl pyrazoles, phenylpyrrazolin class, phenyl pyridazine class, phosphinic acids Class, phosphoramidic acid esters, dithio acid esters, phthalamic acid esters, pyrazoles, pyridazinone, pyridines, pyridine Carboxylic acids, pyridine carboxamides class, hybar X class, pyrimidine radicals (thio) benzoates, quinoline carboxylic acid, semicarbazone class, Sulfonyl-amino-carbnyl triazolinone class, sulfonylurea, Tetrazoline series, thiadiazole, thiocarbamates, triazines, Triazinone, triazole type, triazolineone, triazol carboxyl acylamide, triazolo pyrimidine class, three ketones, uracil or ureas.

By the way that compound of formula I is selected from A at least one)-N) group active material together with apply, available collaboration increasing Imitate the simple adduction (synergistic mixture) that plant health effects are greater than independent effect to get the effect arrived.

This can be by simultaneously, that is, combining (such as tank mix) or separated, or successively apply compound I and at least one It plants other active materials and obtains, wherein the time interval between each application is selected to exist with the active material for ensuring initial application Active position is still present in sufficient amount when applying other active materials.Order of administration is not important to implementation of the invention.

When successively applying compound of formula I and when pesticide I, it is administered twice between time can be between such as 2 hours to 7 days Variation.0.25 hour to 30 days, preferably 0.5 hour to 14 days, especially 1 were even more excellent hour to 7 days or 1.5 hours to 5 days It is also possible for selecting 2 hours to 1 day wider ranges.Comprising the mixture of the pesticide II selected from L) group, preferably agriculture Medicine I is as last processing application.

According to the present invention, solid matter (dry matter) quilt of biological pesticide (other than oily such as neem oil, tagetes oil) It is considered as active component (such as in the case where the liquid adjustments of microbial pesticide, in dry or evaporation Extraction medium or suspension It is obtained after medium).

According to the present invention, corresponding extract is based on for the weight ratio of bio-extract such as Quillaia saponaria extract and percentage herein The total weight of the dry content (solid matter) of object.

Comprising in viable microbial cells form (including suspend mode form) at least one microbial pesticide composition it is total Weight ratio can be calculated the total weight of corresponding active component by using the CFU amount of corresponding microorganism and be determined, wherein using Following equation: 1 × 10¹⁰CFU is equal to the total weight of 1 gram of corresponding active component.Colony Forming Unit is viable microbial cells, especially It is the measurement of fungi and bacterial cell.

Above-mentioned active material, its preparation and its for example to the activity of harmful fungoid be it is known (referring tohttp:// www.alanwood.net/pesticides/)；These substances can be commercially available.The compound that is described by IUPAC nomenclature, its system Standby and its pesticide activity be also known (referring to Can.J.Plant Sci.48 (6), 587-94,1968；EP-A 141 317； EP-A 152 031；EP-A 226 917；EP-A 243 970；EP-A 256 503；EP-A 428 941；EP-A 532 022；EP-A 1 028 125；EP-A 1 035 122；EP-A 1 201 648；EP-A 1 122 244, JP 2002316902；DE 19650197；DE 10021412；DE 102005009458；US 3,296,272；US 3,325,503； WO 98/46608；WO 99/14187；WO 99/24413；WO 99/27783；WO 00/29404；WO 00/46148；WO 00/65913；WO 01/54501；WO 01/56358；WO 02/22583；WO 02/40431；WO 03/10149；WO 03/ 11853；WO 03/14103；WO 03/16286；WO 03/53145；WO 03/61388；WO 03/66609；WO 03/ 74491；WO 04/49804；WO 04/83193；WO 05/120234；WO 05/123689；WO 05/123690；WO 05/ 63721；WO 05/87772；WO 05/87773；WO 06/15866；WO 06/87325；WO 06/87343；WO 07/ 82098；WO 07/90624, WO 11/028657, WO 2012/168188, WO 2007/006670, WO 2011/77514；WO 13/047749, WO 10/069882, WO 13/047441, WO 03/16303, WO 09/90181, WO 13/007767, WO 13/010862, WO 13/127704, WO 13/024009, WO 13/024010 and WO 13/047441, WO 13/162072, WO 13/092224, WO 11/135833).

M group listed above commercial compound especially can in The Pesticide Manual, the 16th edition, C.MacBean, It is found in British Crop Protection Council (2013).Online pesticide manual regularly updates and can pass through Http:// bcpcdata.com/pesticide-manual.html is obtained.Another pesticide online data of ISO common name is provided Library is http://www.alanwood.net/pesticides.M.4 anabasine cycloxaprid is by 2010/069266 He of WO WO 2011/069456 it is known that anabasine M.4A.2-otherwise referred to as guadipyr (guadipyr)-by WO 2013/ Known to 003977 and M.4A.3 anabasine (is approved for paichongding in China) as known to WO 2007/101369.Metaflumizone M.22B.1, analog is described in CN 10171577 and M.22B.2 analog is described in CN 102126994.O-phthalic M.28.1 and M.28.2 amides are as known to WO 2007/101540.M.28.3, anthranilamide is described in WO 2005/ In 077943.M.28.4, hydrazide compound is described in WO 2007/043677.Anthranilamide is M.28.5a)- M.28.5d it) and M.28.5h) is described in WO 2007/006670, WO 2013/024009 and WO 2013/024010, adjacent ammonia Yl-benzamide compound is M.28.5i) it is described in WO 2011/085575, M.28.5j) it is described in WO 2008/134969 In, M.28.5k) be described in US 2011/046186 and M.28.5l) be described in WO 2012/034403.Diamides chemical combination M.28.6 and M.28.7 object can be found in CN 102613183.Spiroketals replace cyclic keto-enols derivative M.29.3 by WO 2006/089633 it is known that and the spirocyclic ketoenols derivative that replaces of xenyl M.29.4 as known to WO 2008/067911. Triazolyl phenyl sulfide M .29.5 is described in WO 2006/043635, and is based on bacillus firmus (bacillus Firmus biological control agent) is described in WO2009/124707.Compound under being listed in M.29.6 is M.29.6a)- M.29.6i) it is described in WO 2012/029672, and M.29.6j) and M.29.6k) be described in WO 2013/129688. Nematicide is M.29.8 as known to WO 2013/055584.It is differentOxazoline is M.29.9.a) it is described in WO 2013/050317. It is differentOxazoline is M.29.9.b) it is described in WO 2014/126208.Pyridalyl type analog is M.29.10 by WO 2010/ Known to 060379.Carboxylic acid amides broflanilide and M.29.11.b)-M.29.11.h) be described in WO 2010/018714 simultaneously And carboxylic acid amides is M.29.11i)-M.29.11.p) be described in WO 2010/127926.Pyridyl thiazole class is M.29.12.a)- M.29.12.c) by WO 2010/006713 it is known that M.29.12.d) and M.29.12.e) by WO 2012/000896 it is known that simultaneously And M.29.12.f)-M.29.12.m) as known to WO 2010/129497.Compound is M.29.14a) and M.29.14b) by WO Known to 2007/101369.Pyrazoles are M.29.16.a)-M.29.16h) it is described in WO 2010/034737, WO 2012/ In 084670 and WO 2012/143317, and pyrazoles are M.29.16i) and M.29.16j) be described in US 61/891437.

An embodiment of mixture according to the present invention, at least one pesticide II are selected from the following group L1)-L6):

L1) have it is antifungal, bactericidal, kill the virus and/or the microbial pesticide of plant defense activator activity: budding is short Obstruct mould (Aureobasidium pullulans) DSM 14940 and DSM 14941 (L1.1), bacillus amyloliquefaciens (Bacillus amyloliquefaciens) AP-188 (L.1.2), bacillus amyloliquefaciens plant subspecies (B.amyloliquefaciens ssp.plantarum) D747 (L.1.3), bacillus amyloliquefaciens plant subspecies (B.amyloliquefaciens ssp.plantarum) FZB24 (L.1.4), bacillus amyloliquefaciens plant subspecies (B.amyloliquefaciens ssp.plantarum) FZB42 (L.1.5), bacillus amyloliquefaciens plant subspecies (B.amyloliquefaciens ssp.plantarum) MBI600 (L.1.6), bacillus amyloliquefaciens plant subspecies (B.amyloliquefaciens ssp.plantarum) QST-713 (L.1.7), bacillus amyloliquefaciens plant subspecies (B.amyloliquefaciens ssp.plantarum) TJ1000 (L.1.8), bacillus pumilus (B.pumilus) GB34 (L.1.9), bacillus pumilus (B.pumilus) GHA 180 (L.1.10), bacillus pumilus (B.pumilus) INR-7 (L.1.11), bacillus pumilus (B.pumilus) QST 2808 (L.1.13), simple bacillus (B.simplex) ABU 288 (L.1.14), bacillus subtilis (B.subtilis) FB17 (L.1.15), the mould (Coniothyrium of shield shell Minitans) CON/M/91-08 (L.1.16), drupe plum surprise yeast (Metschnikowia fructicola) NRRL Y- 30752 (L.1.17), than Lay Penicillium notatum (Penicillium bilaiae) ATCC 22348 (L.1.19), than Lay Penicillium notatum (P.bilaiae) ATCC 20851 (L.1.20), than Lay Penicillium notatum (Penicillium bilaiae) ATCC 18309 (L.1.21), streptomyces microflavus (Streptomyces microflavus) NRRL B-50550 (L.1.22), Trichoderma harzianum (T.harzianum)T-22(L.1.24)；

L2) have it is antifungal, bactericidal, kill the virus and/or the biochemical pesticides of plant defense activator activity: Harpin albumen (L.2.1), polygonum cuspidate (Reynoutria sachalinensis) extract (L.2.2)；

L3) there is insecticidal, mite killing, the microbial pesticide for killing spiral shell and/or eelworm-killing activity: bacillus firmus (Bacillus firmus) I-1582 (L.3.1), bacillus thuringiensis (B.thuringiensis Ssp.aizawai) ABTS-1857 (L.3.2), bacillus thuringiensis Kurstaki (B.t.ssp.kurstaki) ABTS-351 (L.3.3), bacillus thuringiensis intend walking first subspecies (B.t.ssp.tenebrionis) NB-176-1 (L.3.5), beauveria bassiana (Beauveria bassiana) GHA (L.3.6), beauveria bassiana (B.bassiana) JW-1 (L.3.7), bulkholderia cepasea category (Burkholderia sp.) A396 (L.3.9), heliothis armigera nuclear polyhedrosis virus (Helicoverpa armigera nucleopolyhedrovirus) (HearNPV) (L.3.10), corn bollworm caryogram are more Angle precursor virus (Helicoverpa zea nucleopolyhedrovirus) (HzNPV) ABA-NPV-U (L.3.11), corn night Moth unlined garment core-shell type polyhedrosis virus (Helicoverpa zea single capsid nucleopolyhedrovirus) (HzSNPV) (L.3.12), Heterohabditis bacteriophora (L.3.13), fumosorosea (Isaria Fumosorosea) Apopka-97 (L.3.14), Metarhizium anisopliae var. Anisopliae (Metarhizium anisopliae Var.anisopliae) F52 (L.3.15), paecilomyces lilacinus (Paecilomyces lilacinus) 251 (L.3.16), quasi- Si Zhawa Pasteurella (Pasteuria nishizawae) Pn1 (L.3.17), Si Shi Little space (Steinernema Carpocapsae) (L.3.18), Si Shi noctuid nematode (S.feltiae) (L.3.19)；

L4) there is insecticidal, mite killing, the biochemical pesticides for killing spiral shell, pheromones and/or eelworm-killing activity: cis- jasmine Ketone (L.4.1), methyl jasmonate (L.4.2), Quillaia saponaria extract (L.4.3)；

L5) have plant stress reduction, plant growth regulator, plant growth promotion and/or output increased active micro- Biological pesticide.

As described above, present invention is particularly directed to a kind of mixture, it includes:

Fertilizer, the composition comprising fertilizer or the particle comprising fertilizer；With

Capsule according to the present invention or capsule suspension liquid.

The mixture is preferably agriculture chemistry mixture, is suitable for agriculture chemistry application.

The compound that term " fertilizer " is interpreted as applying to promote plant and fruit growth.Fertilizer usually passes through soil (be absorbed by plant roots) feeds intake by soil substitute (also to be absorbed by plant roots) or by blade face (to pass through leaf Absorb) application.The term further includes the mixture of the following fertilizer of one or more different types.

Term " fertilizer " can be subdivided into several classifications, comprising: a) organic fertilizer is (by rotten plant/animal substance structure At), b) inorganic fertilizer (being made of chemicals and mineral) and c) contain urea fertilizer.

Organic fertilizer includes fertilizer such as liquid fertilizer, semiliquid fertilizer, biogas manure, barnyard manure or compost made of stalks, slurry, wormcast Fertilizer, peat, seaweed, compost, sewage and guano.Generally also green manuring crop is to have additional nutrients (especially nitrogen) for soil. The organic fertilizer of manufacture includes compost, blood meal, bone meal and marine algae extract.Other examples are enzymic digestion albumen, fish meal and feather Powder.It is another fertility source from decomposition crop residues a few years ago.In addition, natural minerals, such as ore-rock phosphate, potash sulfuric acid Salt and lime stone are also considered as inorganic fertilizer.

Inorganic fertilizer usually passes through chemical method (such as Haber method) manufacture, these methods also use natural sediment, but right They carry out chemical modification (such as concentration double superhosphate).Natural inorganic fertilizer includes Chilean sodium nitrate, ore-rock phosphate, stone Lime stone and former potash fertilizer.

In a particular embodiment, inorganic fertilizer can be NPK fertilizer." NPK fertilizer " is the nothing prepared with suitable concentration Machine fertilizer and comprising 3 kinds of Main Nutrients nitrogen (N), phosphorus (P) and potassium (K) and usually there are also S, Mg, Ca and trace element group It closes.

In a particular embodiment, to can be urea, urea formadehyde, anhydrous ammonia, urea ammonium nitrate (UAN) containing urea fertilizer molten Liquid, urea sulphur, urea base NPK fertilizer or urea ammonium sulfate.It further include that urea is used as fertilizer.Contain urea fertilizer using or providing In the case where material or urea, urease inhibitor as defined above or they, which can particularly preferably be added, additionally to be deposited , or they are applied in combination simultaneously or with containing urea fertilizer.

Fertilizer can in any suitable form, such as solid, cladding or uncoated particle, with liquid or semiliquid shape Formula is provided as sprayable fertilizer or via fertigation etc..

The material of wide scope can be provided to coated fertilizer.Such as coating can be applied to graininess or granular nitrogen (N) Fertile or more nutrient fertilizers.Urea is usually used as to the basic material of most of coated fertilizers.Or ammonium or NPK fertilizer are used as packet Cover the basic material of fertilizer.However, the invention also includes for any fertilizer of coated fertilizer-it is as defined herein-its His basic material.In some embodiments, elementary sulfur can be used as fertilizer coating.The cladding can be by that will melt S spray Mist is on urea granules, and then application sealing wax is carried out with closing the crackle in coating.In another embodiment, S layers can With with organic polymer layers, preferably organic polymer thin layer is covered.

Other included coated fertilizers can be mentioned and reacting resin based polyalcohol on the surface of fertiliser granulates For.Another example for providing coated fertilizer includes using low-permeability polyethylene polymer with high osmosis coated composition.

In a particular embodiment, the composition of the adjustable fertilizer coating and/or thickness are for example to concrete application control Nutrient release rate processed.The nutrients release duration of specific fertilizer for example can be by several thoughtful several monthly variation.It therefore, can be with Nitrification inhibitor is adapted to exist with the mixture of coated fertilizer.Especially it is possible that nutrients release is related to present invention nitrification inhibition The release of agent or the release of adjoint nitrification inhibitor of the present invention.

Coated fertilizer can be used as release and release control fertilizer (CRF) offer.In a particular embodiment, these release and release control fertilizers are complete The urea or N-P-K fertilizer of cladding, they are the scheduled long-term release of homogeneous and usual display.In other embodiments, CRF can be used as can provide containing cladding, uncoated and/or release sustaining component blending release and release control fertilizer product.In some implementations In scheme, these coated fertilizers can additionally include micronutrient.In a particular embodiment, these fertilizer can be shown pre- Fixed chronicity, such as in the case where N-P-K fertilizer.

The additional possible example of CRF includes combination release fertilizer.These fertilizer usually show scheduled release combination (example Such as height/standard/low) and scheduled chronicity.In an exemplary embodiment, N-P-K, the Mg and micronutrient coated completely It can be to combine delivery mode conveying.

It is also feasible that double-contracting coating method or the coated fertilizer based on sequencing release.

In other embodiments, which can be used as slow release fertilizer and provides or may include or containing slow Release fertilizer.The fertilizer for example can be during any suitable time, such as at 1-5 months, during preferably up to 3 months Interior release.The representative instance of the ingredient of slow release fertilizer is IBDU (isobutylidene diurea), such as containing about 31-32% nitrogen, wherein 90% water is insoluble；Or UF, that is, contain the urea-formaldehyde product of about 38% nitrogen, wherein about 70% can be used as water-insoluble nitrogen It provides；Or the CDU (two urea of crotonal) containing about 32% nitrogen；Or the MU (methylene urea) containing about 38-40% nitrogen, wherein 25-60% is usually cold water insolubility nitrogen；Or the MDU (methylenediourea) containing about 40% nitrogen, wherein being cold less than 25% Water insolubility nitrogen；Or the MO (methylolurea) containing about 30% nitrogen, it is commonly used in solution；Or contain about 40% nitrogen DMTU (dimethylene triurea), wherein less than 25% being cold water insolubility nitrogen；Or TMTU (trimethylenetetraurea urea), it can be with Component as UF product provides；Or TMPU (five urea of trimethylene), the component that can also be used as UF product provide；Or usually UT (urea triazinone solution) containing about 28% nitrogen.The fertiliser mixtures can also be long-term formulation fertilizer containing nitrogen, contain acetylene Two ureas and it is at least one be selected from methylene urea, isobutylidene diurea, two urea of crotonal, substituted Triazinone, 1,3- diamino The mixture of other organic nitrogen-containing fertilizer of or mixtures thereof base formyl urea (triuret).

Any one of above-mentioned fertilizer or fertilizer form can be appropriately combined.For example, slow release fertilizer can be used as cladding Fertilizer provides.They can also be combined with other fertilizer or fertilizer type.This applies equally to depositing for nitrification inhibitor of the present invention It can be adapted and therefore can be being provided so that it discharges releasing along with fertilizer with the form and chemical property of fertilizer It puts, such as is discharged in same time or with identical frequency.In addition, the present invention includes and capsule according to the present invention or capsule suspension Liquid or mixture are combined and are optionally further combined with urease inhibitor as defined above as defined above Fertilizer or fertilizer form.Such combination can provide in the form of coating or is uncoated and/or with sustained release or fast release form.It is excellent The combination of choosing and the slow release fertilizer for including coating.In other embodiments, different release embodiments are also used, such as more slowly Or faster release.

Terms used herein " fertigation " is related to producing fertilizer, optional soil conditioner and other optional water solubilitys Product pass through irrigation system together with water and are applied to plant or in which plant growth or the place for being intended to grow or as follows determine The soil substitute of justice.For example, liquid fertilizer or the fertilizer of dissolution can be supplied directly to plant wherein via fertigation Plant growth or the place for being intended to grow.It is also possible to by capsule according to the present invention or capsule suspension liquid or mixture via The place that fertigation is supplied to plant or in which plant growth or is intended to grow.Fertilizer and capsule according to the present invention or capsule Suspension or mixture can provide together, for example, be dissolved in it is identical charging or charging in irrigation material (usually water).? In other embodiments, fertilizer and capsule according to the present invention or capsule suspension liquid or mixture can be put in different times and mention For.For example, fertilising material can be dripped first, then drop applies nitrification inhibitor, or can preferably drip first and apply nitrification inhibitor, so Drop fertilising material afterwards.These movable time intervals follow above to application fertilizer and capsule according to the present invention or capsule suspension liquid Or time interval described in mixture.It is also feasible that repeat drop fertilising material and capsule according to the present invention or capsule suspension liquid or Mixture or together or intermittently, such as every 2 hours, 6 hours, 12 hours, 24 hours, 2 days, 3 days, 4 days, 5 days, 6 days Or it is longer.

In particularly preferred embodiments, which is containing ammonium fertilizer.

Agriculture chemistry mixture of the present invention may include a kind of fertilizer as defined above and glue as defined above Capsule or capsule suspension liquid.Term mixture is interpreted as covering fertilizer or composition or particle comprising fertilizer, uses basis Capsule of the invention or capsule suspension liquid cladding or processing.

In other embodiments, it is as above to may include at least one or more than one to agriculture chemistry mixture of the invention Fertilizer defined in text, such as 2,3,4,5,6,7,8,9,10 or more different fertilizer (including it is inorganic, organic and contain urea Fertilizer).

Other than fertilizer and capsule as defined above or capsule suspension liquid, agriculture chemistry mixture may include other Ingredient, compound, reactive compound or composition etc..For example, the agriculture chemistry mixture can additionally contain or comprise or base In carrier, such as agriculture chemistry carrier, agriculture chemistry carrier preferably as herein defined.In other embodiments, the agriculture Industry chemical mixture can further include at least one agricultural chemical compound.For example, the agriculture chemistry mixture can be wrapped additionally Containing at least one herbicides compounds and/or at least one Fungicidal compounds and/or at least one Pesticidal compound.

Terms used herein " plant " further comprises all parts of plant, as germinating seed, emergence rice shoot, plant are numerous Grow body, herbaceous plant and the xylophyta of field planting, including all subsurface parts (such as root) and upper portion.

In the context of method for reducing nitrification, it is assumed that plant growth is on soil.In in a particular embodiment, plant Object can also be grown in different ways, such as be grown in compound experiment room environmental or in soil substitute, or can be passed through Artificial or technological means supplement nutrient, water etc..Under such situation, the present invention include processing to be wherein supplied to plant nutrient, The region of water etc. or range.It is also feasible that plant growth is in greenhouse or similar indoor equipment.

Term " place " is interpreted as wherein plant growth or any type environment for being intended to grow, soil, soil substitution Object, region or material.It is preferred that the term is related to the soil or soil substitute that plant grows on it.

Term " plant propagation material " is understood to mean that all reproductive parts such as seed of plant, and can be used for numerous Grow asexual the vegetable material such as cutting and stem tuber (such as potato) of plant.This include seed, grain, root, fruit, stem tuber, bulb, Rhizome, cutting, gemma, branch, spray, bud and other plant part, including after sprouting or emergence after by soil transferring seedling Seedling and seedling, separate living tissue, single and more plant cell and any other the plant tissue of full plants can be obtained by it.

Terms used herein " soil substitute " relates to allow plant growth and does not include the base of conventional soil constituent Matter.The matrix is usually the inorganic matrix that can have the function of inert media.In certain embodiments, it may also contain Organic element or part.Soil substitute for example can be used for hydroponics or solution culture method, i.e., wherein plant growth exists In soil-less culture medium and/or aquatic environment.The example for the suitable soil substitute that can be used in the context of the present invention It is perlite, gravel, biological carbon, mineral wool, cocoanut shell, phyllosilicate, i.e. sheet silicate mineral, usually by with Si₂O₅Or The tetrahedral parallel plate of the silicate of 2:5 ratio is formed or the expansion of clay agglomerates, especially diameter about 10-40mm are viscous Native aggregation.Particularly preferably use vermiculite, i.e., each there are octahedral sheet have 2 tetrahedral sheets phyllosilicate.

In a particular embodiment, the use of soil substitute can be with fertigation as herein defined or irrigation group It closes.

In a particular embodiment, processing can be in all proper growth phase process of plant as herein defined It carries out.For example, processing can carry out during the growth phase of BBCH principle.

Term " growth phase of BBCH principle " is related to the BBCH standard of extension, is all unifacial leaves of uniform encoding and double The class phenology of cotyledon plant kind like the system of growth phase, wherein the entire development cycle of plant be subdivided into it is clearly recognizable and The longer continued development stage distinguished.BBCH standard uses coded decimal system, is divided into main and secondary growth phase. The BBCH that abridges is derived from the Federal Biological Research Centre for Agriculture and Forestry (Germany), the Bundessortenamt (Germany) and chemical industry.

In one embodiment, the present invention relates to it is a kind of reduce nitrification method, including plant GS 00-GS > Between BBCH 99, growth phase (GS) between the GS 00-GS 65BBCH of preferred plant (such as when harvesting apple in the fall When applying fertilizer later) with capsule as defined above, capsule suspension liquid or mixture handle be grown in soil or soil substitute On plant and/or wherein plant growth or be intended to grow place.

In one embodiment, the present invention relates to a kind of methods for reducing nitrification, including the GS 00-GS 45 in plant Between, growth phase (GS) capsule as defined above, capsule suspension liquid or mixed between preferably GS 00-GS 40BBCH It closes object and handles the plant being grown in soil or soil substitute and/or wherein plant growth or the place for being intended to grow.

In preferred embodiments, the present invention relates to a kind of methods for reducing nitrification, including the early growth rank in plant Section (GS), especially GS 00-GS 05 perhaps GS 00-GS 10 perhaps GS 00-GS 15 perhaps GS 00-GS 20 or GS 00-GS 25 or GS 00-GS 33BBCH is handled with capsule as defined above, capsule suspension liquid or mixture and is grown in Plant on soil or soil substitute and/or wherein plant growth or the place for being intended to grow.In particularly preferred embodiment party In case, the method for reduction nitrification including such as being determined during the growth phase including GS 00 at least one above The nitrification inhibitor of justice handles the plant being grown in soil or soil substitute and/or wherein plant growth or is intended to growth Place.

In another embodiment of the present invention, the growth phase between the GS 00-GS 55BBCH of plant will As defined above capsule, capsule suspension liquid or mixture, be applied to the plant being grown in soil or soil substitute and/ Or in which plant growth or be intended to grow place.

In another embodiment of the present invention, the growth phase between the GS 00-GS 47BBCH of plant will be as above Capsule, capsule suspension liquid defined in text or mixture, be applied to the plant being grown in soil or soil substitute and/or its Middle plant growth or the place for being intended to grow.

In one embodiment of the invention, before planting with sowing when, before emergence and until harvest (GS 00-GS 89BBCH), or growth phase (GS) between the GS 00-GS 65BBCH of plant is by glue as defined above Capsule, capsule suspension liquid or mixture, be applied to the plant being grown in soil or soil substitute and/or wherein plant growth or It is intended to the place grown.

In preferred embodiments, the present invention relates to it is a kind of reduce nitrification method, including with capsule, capsule suspension liquid or Mixture handles the plant being grown in soil or soil substitute and/or the wherein place of plant growth, wherein additionally to plant Object and/or wherein plant growth or the place for being intended to grow provide at least one fertilizer.The fertilizer can be any suitable fertilizer Material, fertilizer preferably as defined above.It is also feasible that application more than one fertilizer, such as 2,3,4,5,6,7,8,9,10 kind Fertilizer or different fertilizer type or classification.

In specific embodiments of the present invention, growth phase between the GS 00-GS 33BBCH of plant by capsule, Capsule suspension liquid or mixture and at least one fertilizer be applied to the plant being grown in soil or soil substitute and/or Wherein plant growth or the place for being intended to grow.

In specific embodiments of the present invention, growth phase between the GS 00-GS 55BBCH of plant by capsule, Capsule suspension liquid or mixture and at least one fertilizer be applied to the plant being grown in soil or soil substitute and/or Wherein plant growth or the place for being intended to grow.

In other specific embodiments of the invention, when sowing, emergence before or plant GS 00-GS > Between BBCH 99, growth phase (GS) between preferably GS 00-65BBCH (such as the fertilising after harvest apple in the fall When), preferably capsule, capsule suspension liquid or mixture, and at least one fertilizer are applied to and are grown in soil or soil substitution Plant on object and/or wherein plant growth or the place for being intended to grow.

Preferred embodiment according to the present invention, capsule, capsule suspension liquid or mixture and fertilizer as defined above Application simultaneously carry out or with certain time lag progress.

Terms used herein " time lag ", which refers to be applied to capsule, capsule suspension liquid or mixture before fertilizer, to be grown in Plant on soil or soil substitute and/or wherein plant growth or the place for being intended to grow；Or in capsule, capsule suspension Fertilizer is applied to the plant being grown in soil or soil substitute and/or wherein plant growth or meaning before liquid or mixture The place to be grown.The time lag, which can be, still to be allowed to provide any right times phase of nitrification inhibitory effect in Fertilizer application Between.For example, the time lag can be 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks, 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 Month, during 9 months, 10 months or longer time or during falling into any time between during the time.It is preferred that this when Stagnant is 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks interval.The time lag is preferably directed to wherein applying fertilizer as defined above 1 day before, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks, 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11 weeks, 12 weeks, 4 months, 5 months, 6 months, 7 months, 8 months, 9 months, 10 months or more The situation of nitrification inhibitor as defined above is provided during any time between during growing or falling into the time.

In another embodiment of the present invention, between the GS 00-GS 33BBCH of plant, or in plant Capsule, capsule suspension liquid or mixture are applied between GS 00-GS 65BBCH, condition is at least one fertilizer as defined above The application of material was at least 1 day time lag, such as 1 day, and 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 It, 13 days, 14 days, 3 weeks, 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks or longer or falls between during the time Time lag during any time carries out.It is preferred that the capsule applied between the GS 00-GS 33BBCH of plant, capsule suspension liquid or Mixture is 1 day before applying fertilizer as defined above, and 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 It, provides for 12 days, 13 days, 14 days, 3 weeks, 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks, 11 weeks or 12 weeks.

In another embodiment of the present invention, between the GS 00-GS 33BBCH of plant or the GS of plant At least one fertilizer as defined above is applied between 00-GS 65BBCH, condition is capsule, capsule suspension liquid or mixture Application at least 1 day time lag, such as 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days, 10 days, 11 days, 12 days, 13 days, 14 days, 3 weeks, 4 weeks, 5 weeks, 6 weeks, 7 weeks, 8 weeks, 9 weeks, 10 weeks or longer or during falling into the time between appoint When between during time lag carry out.

Specific embodiment according to the present invention by the plant being grown in soil or soil substitute and/or is wherein planted Place capsule of the present invention, capsule suspension liquid or the mixture that object grows or is intended to grow are handled at least successively.Of the invention In another specific embodiment, by the plant being grown in soil or soil substitute and/or wherein plant growth or it is intended to raw Long place capsule of the present invention, capsule suspension liquid or mixture are handled at least once, and with fertilizer as defined above Processing is at least once.

Term " at least once " refers to that the application can carry out once, or several times, it can including with nitrification inhibitor And/or fertilizer reprocessing.The repetition can be 2 times, 3 times, 4 times, 5 times, 6 times, 7 times, 8 times, 9 times, 10 times or more frequently It repeats to use nitrification inhibitor and/or soil fertility quality.In addition, repeating with capsule of the present invention, capsule suspension liquid or mixture and fertilizer Processing can be different.For example, it is primary only to apply fertilizer, but capsule of the present invention, capsule suspension liquid or mixed can be applied Close object 2 times, 3 times, it is 4 inferior.Alternatively, it is primary only to apply capsule of the present invention, capsule suspension liquid or mixture, but can apply Fertilizer 2 times, 3 times, it is 4 inferior.It further comprise different number repetitive administrations capsule of the present invention, capsule suspension as defined above All combinations of liquid or mixture and fertilizer.

The reprocessing can be further between aforementioned present invention capsule, capsule suspension liquid or mixture and soil fertility quality Time lag combination.

The first time of capsule, capsule suspension liquid or mixture and/or fertilizer of the present invention applies and second or then application Between time interval can be any appropriate interval.The interval can be several seconds to 3 months, such as several seconds to 1 month, or Several seconds to 2 weeks.In other embodiments, which can be several seconds to 3 days or 1 second to 24 hours.

In other specific embodiments, the method as described above for reducing nitrification passes through at least one as determined above The agriculture chemistry mixture of justice handles the plant being grown in soil or soil substitute and/or wherein plant growth or is intended to raw Long place and carry out.

In another embodiment of the present invention, before planting with when, before emergence and until GS > BBCH of plant 99 (such as when applying fertilizer after harvest apple in the fall) applications are comprising containing ammonium or containing urea fertilizer and glue as defined above The agriculture chemistry mixture of capsule or capsule suspension liquid.In packaging kit or conduct of the agriculture chemistry mixture as each section In the case that non-physical mixture provides, it can be to apply between capsule or capsule suspension liquid and fertilizer or application capsule or glue Time lag application between capsule suspension and second or other compositions, such as agricultural chemical compound as described above.

In another embodiment, (together or separate) or propagulum is successively handled preferably simultaneously.

Term " brood body " or " propagulum " are understood to mean that any structure that can obtain new plant, such as plant If son, gemma are separated from parent, it is capable of the vegetative propagation body portion of independent growths.In preferred embodiments, term " breeding Body " or " propagulum " indicate seed.

For the above method or for purposes of the present invention, particularly with being applied in seed treatment and ditch dug with a plow, glue of the present invention The rate of application of capsule, capsule suspension liquid or mixture depends on concrete activity ingredient and processed plant of the different parameters such as application Kind be 0.01g-5kg active constituent/hectare, preferably 1g-1kg active constituent/hectare, particularly preferred 50-300g active constituent/ Hectare.In seed treatment, usually require that the amount of nitrification inhibitor is 0.001-20g/kg seed, preferably 0.01-10g/kg kind Son, more preferable 0.05-2g/kg seed.

It certainly, if can be with effective and non-plant using capsule of the present invention, capsule suspension liquid or mixture, active constituent Toxicity amount uses.This means that compound of formula I is to allow to obtain required effect but not to plant processed or by breeding processed Body or soil processed or soil substitute growing plants cause the amount of any phytotoxicity symptom to provide.For of the invention Purposes, the N amount that the rate of application of fertilizer can choose to make application is 10-1000kg/ha, preferably 50-700kg/ha.

Capsule, capsule suspension liquid or mixture of the present invention are to plant propagation material, especially seed, plant and/or wherein Plant growth or be intended to grow place method of administration be known in the art and the seed dressing including propagation material, coating, Method of administration in granulation, dusting, immersion and ditch dug with a plow.In preferred embodiments, by not inducing the method for sprouting, such as pass through Capsule of the present invention, capsule suspension liquid or mixture are applied on plant propagation material by seed dressing, granulation, coating and dusting.

On the other hand, the composition the present invention relates to a kind of processing fertilizer or comprising fertilizer or particle are to obtain this hair The method of bright mixture.The processing includes capsule according to the present invention or capsule suspension liquid being applied to fertilizer or comprising fertilizer Composition or particle.Therefore the processing may cause in the preparation of fertilizer or other compositions that there are capsule or capsule suspensions Liquid.The processing for example may cause capsule or capsule suspension liquid is uniformly distributed in fertilizer formulations or in fertilizer formulations.Processing side Method is known to the skilled artisan and for example may include seed dressing, coating, granulation, dusting or immersion.In a particular embodiment, The processing can be with fertilizer formulations coated capsule or capsule suspension liquid, or with capsule or capsule suspension liquid coated fertilizer.It should Processing can be based on the use of prilling process known to the skilled artisan, such as fluidized bed prilling.

In another embodiment, the present invention relates to a kind of methods of processing seed or plant propagation material.Herein Term " seed treatment " used is related to or including controlling the biotic stress on seed or in seed and improving plant by germination The step of with development.For seed treatment, it is apparent that by biotic stress such as fungi or insect infestations or be difficult to obtain Enough to the plant of suitable nitrogen source show the sprouting and emergence of reduction, and therapeutic or prevention is carried out to related pest Property processing and can be damaged as caused by the biotic stress factor growing plants propagation material compare, this causes worse Plant or crop establishment and vigor, therefore yield is caused to reduce.Therefore, seed or plant propagation material are handled according to the present invention Method especially plant health is caused to improve, and plant products more preferable to the protection of biotic stress improve.

Capsule of the present invention or capsule suspension liquid or mixture and secondary influences factor such as pesticide, especially fungicide kill The method for treating seeds of worm agent and/or nematicide and/or bioenergizer to the application of plant propagation material, especially seed Be known in the art and the seed dressing including propagation material, coating, coating, granulation and impregnate method of administration.Such method It can be used for present invention combination or composition.

In other embodiments, the processing of seed with capsule according to the present invention or capsule suspension liquid or mixture and Fungicide perhaps insecticide perhaps fungicide and insecticide perhaps fungicide and nematicide or fungicide With biological pesticide and/or bioenergizer perhaps insecticide and nematicide or insecticide and biological pesticide and/or biology Stimulant perhaps nematicide and biological pesticide and/or bioenergizer or fungicide, insecticide and nematicide Combination perhaps the combination of fungicide, insecticide and biological pesticide and/or bioenergizer or insecticide, nematicide and Combination of biological pesticide etc. carries out.

In preferred embodiments, capsule according to the present invention or capsule suspension liquid or mixture pass through so that not negatively The method for influencing to sprout applies on plant propagation material.Therefore, application (or processing) plant propagation material is suitable such as seed The example of method includes seed dressing, seed pelleting or pellet seeds etc..Preferred plant propagation material is seed, cutting (i.e. stem) or kind Ball.

Although it is believed that this method can be applied to the seed of any physiological status, but preferably the seed be in enough persistently and The state that will not be sustained damage during the processing method.The seed is usually the seed harvested by field；It is taken by plant Seed out；And the seed separated with any cob, stem, shell and surrounding pulp or other non-seed vegetable materials.It should Seed preferably goes back Biostatic will not cause the degree of biological damage to the processing to the seed.It is believed that the processing can be in seed It harvests any time between seed sowing or (seed orientation is applied) is applied to seed in seeding process.The seed is also Chromatograph can be applied before and after treatments.

Wish that capsule according to the present invention or capsule suspension liquid or mixture uniformly divide during propagation material processing Cloth and its adhere on seed.Processing can be numerous in plant by the preparaton containing the combination, such as the mixture of active constituent It grows the film (seed dressing) on material such as seed-wherein original size and/or shape can distinguish-and arrives intermediate state (as being coated) so More thick film is arrived afterwards (is permitted multiple layers of different materials (such as carrier, such as clay as having；Different preparatons, not such as other active components Same preparaton；Polymer；And colorant) granulation-wherein original-shape and/or size again cannot be discerned) variation.

One aspect of the present invention includes applying capsule according to the present invention or capsule suspension liquid or mixture in a targeted way In on plant propagation material, this includes making the component distributing in the combination on entire plant propagation material or being distributed only over its portion On point, including being distributed only in single side or in a part of single side.Those skilled in the art will appreciate that coming from These method of administration of the specification provided in EP954213B1 and WO06/112700.

The application of capsule according to the present invention or capsule suspension liquid or mixture on plant propagation material further includes passing through One or more particles containing pesticide and nitrification inhibitor (NI) are placed close to the seed of pesticide-and NI processing and are protected with this The plant propagation material of invention combined treatment, wherein the amount of pesticide should make the seed of pesticide-treated and particle containing pesticide together Pesticide containing effective dose and maximum non-plant of the contained pesticide dosage less than or equal to the pesticide in the seed of the pesticide-treated Object toxicity dose.Such technology is in the art, known especially in WO 2005/120226.

By these combined administrations in further including the controlled release coat on seed on seed, the ingredient incorporation of wherein these combinations It discharges in the material of these ingredients at any time.The example of controlled release seed processing technology it is commonly known in this field and including Thin polymer film, wax or other seed pelletings, wherein these ingredients are mixed in controlled-release material or are applied between material layer, or Person has both the two.

Seed treatment is carried out to seed is not sowed, and term " not sowing " is intended to cover in seed harvest and seed sowing The seed in any period between plant is sprouted and grown in soil.

To the processing for not sowing seed be not intended to include wherein active constituent be applied to soil or soil substitute that A little practices, but including being practiced in plantation technical process by any application of target of seed.

It is preferred that the processing carries out before seed sowing, so that the seed sowed glue according to the present invention Capsule or capsule suspension liquid or mixture processing.Particularly preferred seed pelleting or pellet seeds in the processing of the present composition. As the processing as a result, the ingredient in each combination is attached on seed and therefore can be used for control of insect.

Seed processed can store in such a way that the seed handled with any other active constituent is identical, dispose, sow And cultivation.

Application can before planting or among carry out.Capsule according to the present invention or capsule suspension liquid or mixture are existed The method applied or handled on plant propagation material, especially seed includes seed dressing, coating, granulation, dusting, the leaching of propagation material Method of administration in bubble and ditch dug with a plow.It is preferred that by not inducing the method for sprouting, such as by seed dressing, granulation, coating and dusting by root It is applied on plant propagation material according to capsule or capsule suspension liquid of the invention or mixture.

Ingredient needed for pre-composition preparaton for seed treatment generally comprises 0.5-99.9%, especially 1-95% and 99.5-0.1%, especially 99-5% solid or liquid adjuvants (for example including solvent such as water), wherein auxiliary agent, which can be, is based on being somebody's turn to do Pre-composition preparaton is the surfactant of 0-50%, especially 0.5-40%.However, commercial product is preferably formulated to concentrate (such as premix composition (preparaton), end user is usually using dilution preparaton (such as bucket mixing composition).

When in plant protection, the type that the application total amount of active component depends on required effect is 0.001- 10kg/ha, preferably 0.005-2kg/ha, more preferable 0.05-0.9kg/ha, especially 0.1-0.75kg/ha.Rate of application can be About 1 × 10⁶-5×10¹⁵(or bigger) CFU/ha.It is preferred that spore concentration is about 1 × 10⁷-1×10¹¹CFU/ha.In (Insect Pathogenic Property) nematode as microbial pesticide (such as Ten-spotted lema (Steinernema feltiae)) in the case where, rate of application is excellent It is selected as about 1 × 10⁵-1×10¹²(or bigger), more preferable 1 × 10⁸-1×10¹¹, even more preferably 5 × 10⁸-1×10¹⁰Individual (such as in ovum, larva or any other life phase form, preferably non-reproductive ability (infetive) larval stage)/ha.

When for by the plant protection of seed treatment, capsule according to the present invention or capsule suspension liquid or mixture Amount (total weight based on active component) be 0.01-10kg, preferably 0.1-1000g, more preferable 1-100g/100kg plant is numerous Grow material (preferred seed).1 × 10 is preferably from about for the rate of application of plant propagation material⁶-1×10¹²(or bigger) CFU/ kind Son.Preferred concentration is about 1 × 10⁶-1×10¹¹CFU/ seed.Alternatively, 1 can be about for the rate of application of plant propagation material × 10⁷-1×10¹⁴(or bigger) CFU/100kg seed, preferably 1 × 10⁹To about 1 × 10¹¹CFU/100kg seed.

Embodiment

Following abbreviation used herein and term:

Embodiment 1

It is prepared by the polyvinyl alcohol polyurea capsules suspension 1 stable as protecting colloid according to following programs:

The water phase comprising water and protecting colloid PVA (10wt%) is introduced as initial charge at RT.In stirring condition Under, the charging 1 of the compound A-10 comprising polyisocyanates and table 1 is added, and mixture is dispersed in by water phase with 15,000rpm Middle 3min.Tetraethylenepentamine solution (25wt%) 15min is added under stiring.Mixture is further heated to 80 DEG C and is kept 1h, and 1h is kept at the same temperature, then it is further cooled to RT.The solid content of the dispersion of acquisition is 28.5wt%, Average particle size (D0.5) is 6.66 μm.

Embodiment 2

By the polyvinyl alcohol polyurea capsules suspension 2 stable as protecting colloid to be similar to according to institute in embodiment 1 It states the mode of program and is prepared by being related to ingredient provided below, introduced the difference is that water phase is low at 20 DEG C or more.

The solid content of the dispersion of acquisition is 23.1wt%, and average particle size (D0.5) is 8.66 μm.

Embodiment 3

By the polyvinyl alcohol polyurea capsules suspension 3 stable as protecting colloid to be similar to according to institute in embodiment 1 It states the mode of program and is prepared by being related to ingredient provided below, the difference is that water phase introduces at 20 DEG C.

The solid content of the dispersion of acquisition is 29.6wt%, and average particle size (D0.5) is 8.47 μm.

Embodiment 4

By the polyvinyl alcohol polyurea capsules suspension 4 stable as protecting colloid to be similar to according to institute in embodiment 1 It states the mode of program and is prepared by being related to ingredient provided below, the difference is that water phase introduces at 20 DEG C.

The solid content of the dispersion of acquisition is 33.7wt%, and average particle size (D0.5) is 7.56 μm.

Embodiment 5

It is prepared by pickering particle stabilized polyurea capsules suspension 5 according to following programs:

Comprising water and silica gel, MHPC and HNO will be included at RT₃Pickering system water phase as initial charge It introduces.Under stiring, the compound A-10 of table 1 is added and mixture is dispersed in by 3min in water phase with 21,000rpm.It is stirring Lower addition TEPA solution 15min.Mixture is further heated to 80 DEG C and keeps 1h, and keeps 1h at the same temperature, into One step is cooled to RT.The solid content of the dispersion of acquisition is 20.3wt%, and average particle size (D0.5) is 4.78 μm.

Embodiment 6

By pickering particle stabilized polyurea capsules suspension 6 to be similar to the program according to embodiment 5 Mode and by using ingredient provided below prepare:

The solid content of the dispersion of acquisition is 30.7wt%, and average particle size (D0.5) is 4.97 μm.

Embodiment 7

By pickering particle stabilized polyurea capsules suspension 7 to be similar to the program according to embodiment 5 Mode and by using ingredient provided below prepare:

Water phase is added at 20 DEG C.When introducing charging 2, heating schedule used are as follows: add reaction mixture in 60min Heat is to 65 DEG C；It is heated to 90 DEG C in 60min and keeps reaction mixture 90min at 90 DEG C.When the holding reaction at 90 DEG C When mixture, TEPA is added in reaction mixture.

The solid content of the dispersion of acquisition is 22.5wt%, and average particle size (D0.5) is 2.67 μm.

Embodiment 8

The solid content of the dispersion of acquisition is 11.5wt%, and average particle size (D0.5) is 25.4 μm.

Embodiment 9

Melamine formaldehyde capsule suspension 9 is prepared according to following programs:

It will be comprising water, poly- (2- acrylamide-2-methylpro panesulfonic acid) sodium salt and comprising anti-with formaldehyde at lower than 20 DEG C The water phase of the aqueous solutions of polymers for the 1,3,5- triazine -2,4,6- triamine (70 weight % concentration) answered is introduced as initial charge. Mixture is simultaneously dispersed in 3min in water phase with 21,000rpm by the compound A-10 of addition table 1.It is added comprising aqueous formic acid Charging 2 with by pH stable be 4.Continue to stir 2min.Mixture is further heated to 80 DEG C and keeps 1h, and in Xiang Tongwen Degree is lower to keep 1h, is further cooled to RT.The solid content of the dispersion of acquisition is 21.8wt%, and average particle size (D0.5) is 77.98μm。

Embodiment 10

Melamine formaldehyde capsule suspension 9 by be similar to the program according to embodiment 9 in a manner of and by using Ingredient preparation provided below:

The solid content of the dispersion of acquisition is 27.2wt%, and average particle size (D0.5) is 29.82 μm.

Embodiment 11

It is prepared by the stable polyurea capsules suspension of lignosulfates according to following programs:

Introduce the water phase comprising water and sodium lignosulfate.Under stiring, compound A-10, MDI- base comprising table 1 is added Mixture is simultaneously dispersed 3min with 5000rpm by the mixture of the Pluronic PE 6800 of polyisocyanates and butanol derivs.Into one Step is added DETA and stirs the mixture for 25min.Mixture is futher stirred into 1h at 25 DEG C, is cooled to RT, further plus Enter glycerol and thickener xanthan gum.

The active constituent that dispersion contains is 305g/l, and average particle size (D0.5) is 3.3 μm.

Embodiment 12

The side of the program according to embodiment 11 is similar to by the stable polyurea capsules suspension of sodium lignosulfate Formula and by using ingredient provided below prepare:

The active constituent that suspension contains is 305g/l, and average particle size (D0.5) is 2.5 μm.

Embodiment 13

Non-encapsulated lotion containing reactive compound -10 (table 1) is prepared according to following programs:

The water phase comprising water and Soprophor 4D384 is introduced at 20 DEG C.Under stiring, be added thickener xanthan gum and Mixture is simultaneously dispersed 3min with 5000rpm by compound -10.The active component content that the lotion of acquisition contains is 300g/l (weight Amount), average particle size (D0.5) is 1.2 μm.

Embodiment 14

Soil (100g) is fitted into plastic bottle (500ml) to (for example, the soil sampled from crop field), and moistened to 50% water-holding capacity.Soil is cultivated one week at 20 DEG C, to activate microbial biomass.It is added into soil and contains debita spissitudo (usually 0.3 or 1% nitrogen N) activity test compound -10 or DMSO and the nitrogen (10mg) in ammonium sulfate-N form glue The testing liquid (1ml) of capsule suspension 1-12, and be sufficiently mixed.Bottle is capped, but very loose, to allow air exchange.Then Bottle is cultivated 0,14 or 28 day at 20 DEG C.Identical program is carried out using the non-encapsulated lotion comprising test compound -10.

By K₂SO₄Solution (1%) (300ml) is added in the bottle containing soil, and with 150rpm in horizontal shaker Shake 2h.Entire solution (Macherey-Nagel filter MN 8071/4) is filtered, and at 550 nm in automatic analyzer Ammonium and nitrate content in (Merck, AA11) in analysis filtrate.

(indicating with %) is inhibited to be calculated by formula [(a-b)/(a-c)] x100；Wherein a is to be free of activity test at the end of cultivating Nitrate-nitrogen amount under the test capsule suspension liquid of compound -10；B is compound containing activity test -10 at the end of cultivating Test nitrate-nitrogen amount under capsule suspension liquid.C is nitrate-nitrogen amount when starting.Testization is provided in the following table 2 herein Close the optimal inhibition value that object obtains:

ND- is not surveyed

Compared with the non-encapsulated lotion comprising testing compound, encapsulating capsule suspension liquid shows that improved nitrification inhibits to live Property.Nitrification inhibitory activity further maintains to extend the time.

Embodiment 15

Green head lettuce (green head lettuce) is sowed in Seeding box.Once reaching for 4 leaf stages, one plant is planted Object is put into 8cm basin Plays greenhouse soil (mixture of peat, loam and sand), and in greenhouse under 20 DEG C and 60% humidity Middle growth.After a week, each basin is separated and each basin is placed on design the interior compartment and filling for being used to accommodate basin to planting plants On the plant tray for having the external rings of water.At time 0, will with or without various concentration fertilizer and have empty preparaton or The water for preparing capsule suspension liquid is applied to plant so that the water-holding capacity of soil is about 50%.Then so that edge is placed in fills out The mode that sealed chamber is generated in ring filled with water, gas sample chamber is placed on plant tray, by extracting 20cc out in the room Air empties in Vacutainer (Labco, 12ml volume) into syringe and immediately.This be equal to each basin time 0 when Measured value.Identical program is carried out to all basins in test.After 1h cultivates the time, again as described above from gas compartment It takes out 20cc air sample and is emptied in Vacutainers.Then plant is back at its position in the greenhouse.It is connecing Get off in a couple of days, accurately in daily synchronization program, until N₂O drains back into background level.

Sample is analyzed in the Shimadzu 2014GC for being equipped with ECD system.Calculate total accumulation N₂O is discharged and is passed through meter The suppression percentage calculated compared with the control is associated.

The capsule suspension liquid prepared according to embodiment 4-6	Inhibit (%) N₂O discharge
		4	31.44
6	56.93
		Activity test compound -10 (is not prepared)	Inhibit (%) N₂O discharge
A-10	25

Encapsulating capsule suspension liquid is reducing N₂O discharge aspect specific activity test compound (not preparing) more effectively, and is made There is the effect of enhancing for nitrification inhibitor.

Claims

1. capsule, it includes:

(1) core (a) and shell (b), center (a) are encapsulated by shell (b)；Or

(2) matrix (c)；

Wherein, if capsule includes core (a) and shell (b) according to option (1), core (a) includes compound of formula I or its alloisomerism Body, salt, tautomer or N- oxide:

Wherein

R¹And R²It is independently selected from H, C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkynyl, C₁-C₆Halogenated alkyl, C₁-C₄Alcoxyl Base-C₁-C₄Alkyl, C₁-C₆Alkoxy, C₂-C₆Alkenyloxy, C₂-C₆Alkynyloxy group, wherein carbon atom in each case can be not It is substituted or can have 1,2 or 3 identical or different substituent R^e；

C₃-C₈Naphthenic base, C₃-C₈Cycloalkenyl, heterocycle, aryl, heteroaryl, C₃-C₈Naphthenic base-C₁-C₆Alkyl, C₃-C₈Cycloalkenyl- C₁-C₆Alkyl, heterocycle-C₁-C₆Alkyl, aryl-C₁-C₆Alkyl and heteroaryl-C₁-C₆Alkyl, phenoxy group and benzyloxy, wherein Cyclic moieties in each case can be unsubstituted or can have 1,2,3,4 or 5 identical or different substitution Base R^a；

A is phenyl, wherein the benzyl ring can be unsubstituted or identical or different can be taken with 1,2,3,4 or 5 For base R^A；

Wherein

C₁-C₆Alkyl, C₂-C₆Alkenyl, C₂-C₆Alkynyl, C₁-C₆Halogenated alkyl, C₁-C₆Alkoxy, C₁-C₆Alkylthio group, wherein carbon Atom in each case can be unsubstituted or can have 1,2 or 3 identical or different substituent R^e；

C₃-C₈Naphthenic base, C₃-C₈Cycloalkenyl, heterocycle, aryl, heteroaryl, C₃-C₈Naphthenic base-C₁-C₆Alkyl, C₃-C₈Cycloalkenyl- C₁-C₆Alkyl, heterocycle-C₁-C₆Alkyl, aryl-C₁-C₆Alkyl and heteroaryl-C₁-C₆Alkyl, phenoxy group and benzyloxy, wherein Cyclic moieties can be unsubstituted or can have 1,2,3,4 or 5 identical or different substituent R^a；

And wherein

Or two substituent Rs on adjacent carbon atom^aIt can be for selected from CH₂CH₂CH₂CH₂、OCH₂CH₂CH₂、CH₂OCH₂CH₂、 OCH₂CH₂O、OCH₂OCH₂、CH₂CH₂CH₂、CH₂CH₂O、CH₂OCH₂、O(CH₂)O、SCH₂CH₂CH₂、CH₂SCH₂CH₂、SCH₂CH₂S、 SCH₂SCH₂、CH₂CH₂S、CH₂SCH₂、S(CH₂) S bridge and with the two R^aThe carbon atom being bonded is formed together 5 Yuans or 6 members Saturated carbon ring or heterocycle；

R^cAnd R^dThe N atom being bonded with them is formed together 5 or 6 Yuans saturations or unsaturated heterocycle, which can have and be selected from O, another hetero atom of S and N as ring members atom and wherein the heterocycle can it is unsubstituted or can with 1,2,3,4 or 5 are independently selected from the substituent group of halogen；

Y is O or S；And

M is 0,1 or 2；

And

Shell (b) includes shell material, is selected from:

(b1) polyaddition products of isocyanates；

(b2) poly- (methyl) acrylate；With

(b3) aminoplast；

And wherein, if capsule includes matrix (c) according to option (2), matrix (c) includes that compound of formula I or its solid are different Structure body, salt, tautomer or N- oxide:

Wherein

And wherein

Y is O or S；And

M is 0,1 or 2；

And host material, it is selected from:

(c1) poly- (methyl) acrylate；With

(c2) calcium alginate.

2. capsule according to claim 1, wherein in the compound of formula I, R¹And R²Respectively H；A is phenyl, wherein described Benzyl ring is unsubstituted or with 1,2 or 3 identical or different substituent R^A, wherein R^AIf present then selected from halogen, C₁-C₄Alkyl and C₁-C₄Alkoxy.

3. capsule according to claim 1 or 2, the vapour pressure of compounds of formula I is at 20 DEG C more than 0.2Pa or even 20 More than 1.0Pa at DEG C.

4. capsule as claimed in one of claims 1-3, wherein capsule includes core (a) and shell (b), and center (a) is by shell (b) Encapsulating, and the weight ratio of core (a) and shell (b) is 70:30-98:2, preferably 80:20-95:5.

5. capsule as claimed in one of claims 1-4, wherein shell material is selected from the polyaddition products of (b1) isocyanates, packet Contain:

(b1c) multifunctional at least one polyfunctional isocyanate of polymerized form and at least one polyfunctional amine and at least one Alcohol.

6. capsule as claimed in one of claims 1-4, wherein shell material is

(b2a) poly- (methyl) acrylate comprising methyl methacrylate and/or methacrylic acid in polymerized form；Or

(b3a) aminoplast comprising melamine and formaldehyde in polymerized form.

7. capsule as claimed in one of claims 1-6, wherein the shell (b) of capsule includes organic or inorganic protecting colloid.

8. capsule as claimed in one of claims 1-7, with following mass median particle size:

- 300 μm or smaller, preferably 50nm-200 μm, more preferable 0.5-50 μm.

9. a kind of capsule suspension liquid, it includes:

It include the suspended phase of capsule as claimed in one of claims 1-8, wherein the mass median particle size of capsule is 300 μm Or it is smaller；With

Liquid phase；

10. a kind of mixture, it includes:

(ii) capsule as claimed in one of claims 1-8 or capsule suspension liquid according to claim 9.

11. capsule as claimed in one of claims 1-8 or capsule suspension liquid according to claim 9 or according to claim Purposes of 10 mixture in agriculture chemistry application, wherein preferably include will be any according to claim 1-8 for the purposes Capsule or capsule suspension liquid according to claim 9 or mixture according to claim 10 be applied to plant root zone, Soil, soil substitute and/or wherein plant growth or be intended to grow place.

12. purposes according to claim 11, wherein the purposes is for reducing nitrification.

13. a kind of method for reducing nitrification, including by capsule as claimed in one of claims 1-8 or according to claim 9 Capsule suspension liquid or mixture according to claim 10 be applied to the root zone of plant, soil, soil substitute and/or wherein Plant growth or the place for being intended to grow.

14. 1 or 12 purposes or method according to claim 13 according to claim 1, wherein to the root zone of plant, soil, Soil substitute and/or wherein plant growth or the place for being intended to grow are additionally provided fertilizer, wherein according to claim 1 in -8 The application of the capsule of any one or capsule suspension liquid according to claim 9 or mixture according to claim 10 and fertilizer It can carry out or be carried out with certain time lag simultaneously, preferably by most 1 day, 2 days, 3 days, 1 week, 2 weeks or 3 weeks.

15. mixture according to claim 10 or method according to claim 14 or purposes, wherein the fertilizer includes:

Solid or liquid inorganic fertilizer containing ammonium, preferably NPK fertilizer, ammonium nitrate, calcium ammonium nitrate, ammonium sulfate nitrate, ammonium sulfate or phosphoric acid Ammonium；

Solid or liquid organic fertilizer, preferred liquid fertilizer, semiliquid fertilizer, biogas manure, barnyard manure and compost made of stalks, compost from earthworm, Compost, seaweed or guano；Or